WO2022126442A1 - 量子点层图案化的方法 - Google Patents

量子点层图案化的方法 Download PDF

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WO2022126442A1
WO2022126442A1 PCT/CN2020/136901 CN2020136901W WO2022126442A1 WO 2022126442 A1 WO2022126442 A1 WO 2022126442A1 CN 2020136901 W CN2020136901 W CN 2020136901W WO 2022126442 A1 WO2022126442 A1 WO 2022126442A1
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layer
quantum dot
sacrificial layer
target area
patterning
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PCT/CN2020/136901
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English (en)
French (fr)
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张晓远
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京东方科技集团股份有限公司
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Priority to PCT/CN2020/136901 priority Critical patent/WO2022126442A1/zh
Priority to CN202080003382.7A priority patent/CN115918298A/zh
Priority to US18/036,383 priority patent/US20230403923A1/en
Publication of WO2022126442A1 publication Critical patent/WO2022126442A1/zh

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
    • H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • 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
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/1201—Manufacture or treatment
    • 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
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/166—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using selective deposition, e.g. using a mask
    • 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
    • H10K71/191—Deposition of organic active material characterised by provisions for the orientation or alignment of the layer to be deposited
    • 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
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • 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

Definitions

  • the present disclosure relates to the field of display technology, and in particular, to a method for patterning a quantum dot layer.
  • Quantum dots also known as semiconductor nanocrystals and semiconductor nanoparticles, refer to nano-solid materials whose dimensions are in the nanometer order in three dimensions of space or are composed of them as basic units. A collection of atoms and molecules. Light-emitting diodes based on quantum dot materials are called quantum dot light-emitting diodes (QLEDs), which are a new type of light-emitting devices.
  • QLEDs quantum dot light-emitting diodes
  • a stacked front film layer and a sacrificial layer are sequentially formed on the substrate; wherein, one of the sacrificial layer and the front film layer is hydrophilic, and the other is hydrophobic;
  • a mask layer with through holes is formed on the sacrificial layer, the through holes correspond to the target area, and the sacrificial layer in the target area is etched under the shielding of the mask layer;
  • the remaining sacrificial layer is removed to form a patterned quantum dot layer in the target area.
  • forming a mask layer with through holes on the sacrificial layer specifically includes:
  • a photoresist is formed on the sacrificial layer, the photoresist is patterned, and the photoresist in the target area is removed to form the mask layer with through holes.
  • the step of sequentially forming a stacked front film layer and a sacrificial layer on the substrate specifically includes:
  • the electron transport layer is the front film layer, and the electron transport layer has hydrophilicity;
  • the sacrificial layer is formed on the side of the electron transport layer away from the substrate; wherein, the sacrificial layer has hydrophobicity.
  • the step of sequentially forming a stacked front film layer and a sacrificial layer on the substrate specifically includes:
  • the cathode is the front film layer, and the cathode has hydrophilicity;
  • the sacrificial layer is formed on the side of the cathode away from the substrate; wherein, the sacrificial layer has hydrophobicity.
  • the method further includes:
  • An electron transport layer is formed.
  • the contact angle between the material of the sacrificial layer and water is greater than 90°.
  • the material of the sacrificial layer has Si-O-Si hydrophobic chains.
  • the material of the sacrificial layer includes at least one of the following: polymethylsilsesquioxane, methacrylamide polysesquioxane Siloxane, polyphenylsilsesquioxane, polydimethylsiloxane, polyfluorosiloxane, polychlorosiloxane.
  • the main chain or branch of the sacrificial layer material has a fluorine-based hydrophobic group of -F or -CF 3 .
  • the material of the sacrificial layer includes at least one of the following: fluoropolystyrene and fluoropolyacrylate.
  • etching the sacrificial layer of the target area under the shielding of the mask layer specifically including:
  • the remaining sacrificial layer and photoresist are removed by solvent soaking or solvent rinsing.
  • the patterning of the photoresist to remove the photoresist in the target area specifically includes:
  • a mask is used to shield the photoresist.
  • the mask includes a light-transmitting area and a light-shielding area. target area;
  • the photoresist of the target area is removed using a solvent.
  • the removing the sacrificial layer in the target area specifically includes:
  • Oxygen plasma is used to etch away the sacrificial layer in the target area.
  • the covering the quantum dot material and curing the quantum dots in the target area specifically includes:
  • the quantum dot material in the target area is irradiated with light of a preset wavelength; wherein, under the irradiation of the light of the preset wavelength, the photosensitive material or the product of the photosensitive material after the irradiation of the light is the same as the
  • the ligands on the surface of the quantum dots react, so that the ligands fall off the surface of the quantum dots, so as to change the solubility of the quantum dots in the target area, so that the quantum dots in the target area are aggregated to solidify the Quantum dots in the target area;
  • the covering quantum dot material and curing the quantum dots in the target area specifically include:
  • the quantum dot material in the target area is irradiated with light of a preset wavelength, so that the quantum dots in the target area are cross-linked, so as to cure the quantum dots in the target area.
  • the material of the electron transport layer includes ZnO, ZnMgO, or ZnAlOx.
  • FIG. 1 is a schematic flowchart of a method for patterning a quantum dot layer according to an embodiment of the present disclosure
  • FIG. 2 is a schematic flowchart of another method for patterning a quantum dot layer according to an embodiment of the present disclosure
  • 3A-3K are schematic structural diagrams of each preparation step in the method for patterning a quantum dot layer according to an embodiment of the present disclosure
  • FIG. 4 is a schematic flowchart of another method for patterning a quantum dot layer according to an embodiment of the present disclosure
  • 5A-5J are schematic structural diagrams of each preparation step in the method for patterning a quantum dot layer according to an embodiment of the present disclosure
  • 6A is a schematic structural diagram of a polymethylsilsesquioxane provided in an embodiment of the present disclosure
  • 6B is a schematic structural diagram of a methacrylamide polysilsesquioxane provided in an embodiment of the present disclosure
  • 6C is a schematic structural diagram of a polyphenylsilsesquioxane provided in an embodiment of the present disclosure
  • Fig. 7 is the synthesis schematic diagram of the structure shown in Fig. 6C;
  • FIG. 8A is a schematic structural diagram of a fluoropolystyrene provided in an embodiment of the present disclosure
  • 8B is a schematic structural diagram of a fluoropolyacrylate provided in an embodiment of the present disclosure.
  • FIG. 8C is a schematic structural diagram of another fluoropolyacrylate provided in an embodiment of the present disclosure.
  • 9A and 9B are schematic diagrams of synthesis of the structure shown in FIG. 8C, respectively;
  • FIG. 10 is a schematic structural diagram of a quantum dot light-emitting device provided by an embodiment of the present disclosure.
  • FIG. 11 is a schematic structural diagram of a quantum dot light-emitting device with an inverted structure provided by an embodiment of the present disclosure
  • FIG. 12 is a schematic structural diagram of a quantum dot light-emitting device with an upright structure according to an embodiment of the present disclosure.
  • the colloidal solution of quantum dots can be patterned by printing, transfer printing, photolithography, etc., but the printing equipment is expensive and the resolution is limited. In recent years, many researchers have done a lot of work on photolithography patterning. Some use the direct lithography method to pattern the quantum dot film layer, that is, the method of cross-linking ligands. Under the irradiation of ultraviolet light, the quantum dot ligands are cross-linked and cured, and the non-cross-linked part can be cured due to its high solubility. The solvent is washed off, but this method is easy to cause color mixing due to the residue of quantum dots when preparing full-color devices.
  • the quantum dots can be peeled off together with the sacrificial layer and the photoresist, and it is not easy to form color mixing; however, in this method, the commonly used sacrificial layer material is poly Vinylpyrrolidone, which is soluble in water and ethanol, has strong hydrophilic properties; for example, for inverted quantum dot devices, before fabricating the patterned quantum dot layer, a sacrificial layer and an electron transport layer can be made on the electron transport layer.
  • Photoresist layer, sacrificial layer and photoresist layer can also be made on the transparent electrode layer, that is, the sacrificial layer is in direct contact with the electron transport layer or the transparent electrode layer, because there are usually hydroxyl groups on the surface of the electron transport layer and the transparent electrode layer.
  • an embodiment of the present disclosure provides a A method for patterning a quantum dot layer, as shown in Figure 1, includes:
  • the affinity between the two materials of the front film layer and the sacrificial layer can be reduced, so that the subsequent sacrificial layer can be reduced.
  • the peeling off from the mask layer becomes easy, and the sacrificial layer and the mask layer can be peeled off without using ultrasonic, so as to maintain the integrity of other film layers of the device where the quantum dot layer is located, thereby improving the performance of the device.
  • covering the quantum dot material and curing the quantum dots in the target area specifically includes:
  • the quantum dot material is covered by one or a combination of spin coating, blade coating, spray coating, ink jet printing, and electrospray printing.
  • forming a mask layer with through holes on the sacrificial layer may specifically include:
  • a photoresist is formed on the sacrificial layer, the photoresist is patterned, and the photoresist in the target area is removed to form a mask layer with through holes. Since the photoresist only needs to be exposed and developed to form a patterned photoresist pattern, the photoresist can be patterned according to the position of the patterned quantum dot layer to be formed, which is simple and convenient to manufacture. Therefore, the embodiment of the present disclosure adopts a pattern The photoresist is used as a mask layer.
  • the mask layer is not limited to being formed by using photoresist.
  • the mask layer can also be a mask layer with a through hole region made of quartz material or metal material.
  • the embodiment of the present disclosure uses a patterned photoresist as a mask layer. Since the photoresist needs to be exposed and developed to form a patterned area, taking negative photoresist as an example, the exposed area remains and is not exposed. The area is developed, and the remaining photoresist will be denatured due to exposure. Generally, acid or alkali is required to clean the exposed photoresist, and the corrosiveness of acid and alkali will destroy the performance of quantum dots.
  • the sacrificial layer is introduced before the resist, and the sacrificial layer can be peeled off by using a common solvent, that is, the sacrificial layer is introduced to better peel off the photoresist, and the sacrificial layer of the present disclosure is opposite to the hydrophilic and hydrophobic properties of the front film layer, so it is not necessary to The sacrificial layer and the photoresist can be peeled off by means of ultrasound, and the integrity of other film layers of the device where the quantum dot layer is located can be maintained, thereby improving the performance of the device.
  • a scheme of sacrificial layer + photoresist as a mask layer is used to fabricate a patterned quantum dot layer.
  • the quantum dots provided by the embodiments of the present disclosure include but are not limited to CdS, CdSe, ZnSe, InP, PbS, CsPbCl 3 , CsPbBr 3 , CsPhI 3 , CdS/ZnS, CdSe/ZnSe, CdSe/ZnS, ZnSe, InP /ZnS, PbS/ZnS, CsPbCl 3 /ZnS, CsPbBr 3 /ZnS, CsPhI 3 /ZnS and other quantum dots.
  • electroluminescent devices can be divided into an upright structure and an inverted structure, and the difference between the upright structure and the inverted structure lies in the fabrication sequence of the film layers.
  • the upright structure is to sequentially form an anode, a hole injection layer, a hole transport layer, a quantum dot layer, an electron transport layer and a cathode on the substrate
  • the inverted structure is to sequentially form an electron transport layer, a quantum dot layer, Hole transport layer, hole injection layer and anode.
  • the embodiments of the present disclosure mainly take a light-emitting device with an inverted structure as an example to describe the method for patterning a quantum dot layer in detail.
  • the embodiment of the present disclosure is also applicable to a method for patterning a quantum dot layer in an upright structure.
  • the quantum dot layer generally includes patterned quantum dots of different colors.
  • the quantum dot layer includes a first quantum dot layer, a second quantum dot layer, and a third quantum dot layer as an example.
  • InP/ZnS quantum dots can be formed by, but not limited to, a solution-phase synthesis method, a hydrothermal method, a solvothermal method, and the like.
  • a stacked front film layer and a sacrificial layer are sequentially formed on the substrate, as shown in FIG. 2 , which may specifically include:
  • a cathode 2 is formed on the substrate 1, and the material of the cathode 2 can be a transparent metal oxide conductive material, such as ITO (indium tin oxide), AZO (aluminum doped zinc oxide), IGZO (indium tin oxide) gallium zinc oxide) etc.
  • the substrate 1 formed with the cathode 2 was washed with water, ethanol and acetone in turn for 10 minutes, then blown dry with an air gun, and treated with ultraviolet ozone for 10 minutes, then, a pixel was formed on the side of the cathode 2 away from the substrate 1 Defining layer 3, the pixel defining layer 3 has a plurality of pixel openings exposing the cathode 2; as shown in FIG.
  • an electron transport layer 4 is formed on the cathode 2 in the pixel opening, and the material of the electron transport layer 4 is generally ZnO, such as in
  • the cathode 2 is spin-coated with 30 mg/ml ZnO nanoparticle solution and annealed at 120°C for 10 minutes. There are usually a lot of hydroxyl groups on the surface of ZnO, so the electron transport layer 4 has strong hydrophilic properties.
  • a sacrificial layer 5 is formed on the side of the electron transport layer 4 away from the substrate 1 .
  • the sacrificial layer 5 is made of a material with hydrophobic properties.
  • polyphenylsilsesquioxane with a molar mass greater than 10 4 g/mol is selected as the sacrificial layer material (the material will be described in detail later), when the molar mass is greater than 10 4 g/mol, the polymer can be dissolved in chlorine Benzene is insoluble in xylene.
  • a photoresist 6 is formed on the sacrificial layer 5 .
  • the photoresist is patterned to remove the photoresist in the target area; specifically, as shown in FIG. 3E , a mask 7 is used to shield the photoresist 6, and the mask 7 includes a light-transmitting area 71 and a light-shielding area 72 , the light-transmitting area 71 corresponds to the reserved area in the photoresist 6 that receives light irradiation, and the light-shielding area 72 corresponds to the first target area A1 for making the first quantum dots; as shown in FIG. 3F, a solvent is used to remove the light of the first target area A1 photoresist. Specifically, since the aforementioned sacrificial layer material is insoluble in xylene, xylene can be used to develop the photoresist in the first target area A1.
  • the sacrificial layer of the first target area A1 is etched under the shielding of the mask layer (photoresist); specifically, the sacrificial layer of the first target area A1 can be etched away by using oxygen plasma .
  • the first quantum dot material 8 is covered on the basis of FIG. 3G , and the first quantum dot material 8 in the first target area A1 is cured.
  • the following method can be used: firstly cover the first quantum dot material 8 with the photosensitive material, for example, after mixing the photosensitive material and the first quantum dot material 8 Covering; then irradiating the first quantum dot material 8 in the first target area A1 with light of a preset wavelength (such as ultraviolet light); wherein, under the irradiation of the preset wavelength of light, the photosensitive material or the photosensitive material generated after the light irradiation The compound reacts with the ligands on the surface of the first quantum dots, so that the ligands fall off from the surface of the first quantum dots, so as to change the solubility of the first quantum dots in the first target area A1, so that the first quantum dots in the first target area A1 Coagulation occurs to solidify the first quantum dots of the first target area A1.
  • a preset wavelength such as ultraviolet light
  • the photosensitive material may include a photoacid generator, an olefinic substance or an alkyneic substance.
  • the photoacid generator when the photosensitive material is a photoacid generator, the photoacid generator generates hydrogen ions under the irradiation of ultraviolet light, and the hydrogen ions are combined with the ligands on the surface of the first quantum dots, so that the ligands are released from the first quantum dots.
  • the surface is peeled off, and the solubility of the first quantum dots without ligands is different from that of the first quantum dots with ligands, so that the first quantum dots without ligands in the first target area A1 can be aggregated, thereby The first quantum dots of the first target area A1 are cured.
  • the photosensitive material is an alkene or alkyne
  • the alkene and alkyne can directly bind to the ligands on the surface of the first quantum dots, so that the ligands fall off from the surface of the first quantum dots, so as to realize the curing of the first quantum dots.
  • the following method can also be used: firstly cover the first quantum dot material 8 with crosslinkable ligands on the surface, and generally prepare the quantum dot surface
  • the first quantum dot material 8 with cross-linkable ligands can be prepared by using a cross-linking reagent to replace the original ligand on the surface of the quantum dots; then a preset wavelength of light (such as ultraviolet light) is used.
  • a preset wavelength of light such as ultraviolet light
  • the remaining sacrificial layer 5 and photoresist 6 are removed, and a patterned first quantum dot layer 81 is formed in the first target area A1. Since the hydrophilic and hydrophobic properties of the sacrificial layer 5 and the electron transport layer 4 are opposite, the affinity between the sacrificial layer 5 and the electron transport layer 4 is poor, so a solvent can be used directly (since the sacrificial layer is soluble in chlorobenzene, the solvent can be chlorine The remaining sacrificial layer 5 and photoresist 6 are removed by immersion in benzene) or solvent (chlorobenzene) rinsing, without the need to use ultrasonic assistance to speed up the stripping process of the sacrificial layer 5 and photoresist 6 as in the related art.
  • the peeling of the sacrificial layer 5 and the photoresist 6 is easier, and the sacrificial layer 5 and the photoresist 6 can be peeled off without using ultrasonic waves, so as to maintain the integrity of the first quantum dot layer 81 and the electron transport layer 4, Thereby improving the performance of the device.
  • a second quantum dot layer 91 is formed in the second target area A2 using the same steps as shown in FIGS. 3C to 3I , as shown in FIG. 3J ; the difference between forming the second quantum dot layer 91 and forming the first quantum dot layer 81 is that Covered is the second quantum dot material.
  • a third quantum dot layer 11 is formed in the second target area A2 using the same steps as shown in FIGS. 3C to 3I , as shown in FIG. 3K ; the difference between forming the third quantum dot layer 11 and forming the first quantum dot layer 81 is that Covered is the third quantum dot material.
  • the patterned quantum dot layers shown in FIGS. 3A to 3K are made with the former film layer as the electron transport layer 4 , that is, the electron transport layer 4 is first formed on the cathode 2 , and then the sacrificial layer 5 and the photoresist are formed. 6 and quantum dot materials are described as examples.
  • a stacked front film layer and a sacrificial layer are sequentially formed on the substrate, as shown in FIG. 4, which can include:
  • a cathode 2 is formed on the substrate 1, and the material of the cathode 2 can be a transparent metal oxide conductive material, such as ITO (indium tin oxide), AZO (aluminum doped zinc oxide), IGZO (indium tin oxide) gallium zinc oxide), etc.
  • the material of the cathode 2 is ITO as an example
  • the substrate 1 on which the cathode 2 is formed is sequentially washed with water, ethanol and acetone for 10 minutes, then dried with an air gun, and treated with ultraviolet ozone for 10 minutes
  • a pixel defining layer 3 is formed on the side of the cathode 2 away from the substrate 1.
  • the pixel defining layer 3 has a plurality of pixel openings exposing the cathode 2. Since the material of the cathode 2 is a transparent conductive material such as ITO, the surface of the ITO usually has a large number of hydroxyl groups. exists, so the cathode 2 has strong hydrophilic properties.
  • a sacrificial layer 5 is formed on the side of the cathode 2 away from the substrate 1 .
  • the sacrificial layer 5 is made of a material with hydrophobic properties.
  • polyphenylsilsesquioxane with a molar mass greater than 10 4 g/mol is selected as the sacrificial layer material (the material will be described in detail later), when the molar mass is greater than 10 4 g/mol, the polymer can be dissolved in chlorine Benzene is insoluble in xylene.
  • the polyphenyl silsesquioxane was dissolved in chlorobenzene to prepare a solution with a concentration of 30 mg/ml, and the polyphenyl silsesquioxane solution was spin-coated on the cathode 2 and left to dry for 10 minutes.
  • a photoresist 6 is formed on the sacrificial layer 5 .
  • the photoresist is patterned to remove the photoresist in the target area; specifically, as shown in FIG. 5C , a mask 7 is used to shield the photoresist 6, and the mask 7 includes a light-transmitting area 71 and a light-shielding area 72 , the light-transmitting area 71 corresponds to the reserved area in the photoresist 6 that receives light irradiation, and the light-shielding area 72 corresponds to the first target area A1 for making the first quantum dots; as shown in FIG. 5D , a solvent is used to remove the light of the first target area A1 photoresist. Specifically, since the aforementioned sacrificial layer material is insoluble in xylene, xylene can be used to develop the photoresist in the first target area A1.
  • the sacrificial layer of the first target area A1 is etched under the shielding of the mask layer (photoresist); specifically, the sacrificial layer of the first target area A1 can be etched away by using oxygen plasma .
  • the electron transport layer 4 is formed on the basis of FIG. 5E .
  • the first quantum dot material 8 is covered on the basis of FIG. 5F , and the first quantum dot material 8 in the first target area A1 is cured.
  • the method of curing the first quantum dot material 8 in the first target area A1 reference may be made to the curing method described above for the step of FIG. 3H , which will not be repeated here.
  • the remaining sacrificial layer 5 and photoresist 6 are removed, and a patterned first quantum dot layer 81 is formed in the first target area A1 .
  • the affinity between the sacrificial layer 5 and the cathode 2 is poor, so a solvent can be used directly (since the sacrificial layer is soluble in chlorobenzene, the solvent can be chlorobenzene) soaking or
  • the remaining sacrificial layer 5 and the photoresist 6 are removed by rinsing with a solvent (chlorobenzene), without the need to use ultrasonic assistance to speed up the stripping process of the sacrificial layer 5 and the photoresist 6 as in the related art.
  • the sacrificial layer is 5 and the photoresist 6 are easier to peel off, the sacrificial layer 5 and the photoresist 6 can be peeled off without the need of ultrasonic, and the integrity of the first quantum dot layer 81 and the electron transport layer 4 is maintained, thereby improving the device performance. performance.
  • the electron transport layer 4 in the area other than the first target area A1 is formed on the photoresist 6, the electron transport layer 4 in the area other than the non-first target area A1 is peeled off, and only the first target area A1 is removed.
  • the target area A1 forms the first quantum dot layer 81 and the electron transport layer 4 .
  • a second quantum dot layer 91 is formed in the second target area A2 using the same steps as shown in FIGS. 5A to 5H , as shown in FIG. 5I ; the difference between forming the second quantum dot layer 91 and forming the first quantum dot layer 81 is that Covered is the second quantum dot material.
  • the second quantum dot layer 91 since the electron transport layer 4 in the area other than the second target area A2 is formed on the photoresist 6, the area not in the area other than the second target area A2 is formed on the photoresist 6. The electron transport layer 4 is peeled off, and the second quantum dot layer 91 and the electron transport layer 4 are formed only in the second target region A2.
  • the selected solvent can only The sacrificial layer is dissolved without dissolving the first quantum dot layer, so as to prevent the loss of the fabricated first quantum dot layer.
  • a third quantum dot layer 11 is formed in the second target area A2 using the same steps as shown in FIGS. 5A to 5H , as shown in FIG. 5J ; the difference between forming the third quantum dot layer 11 and forming the first quantum dot layer 81 is that Covered is the third quantum dot material.
  • the third quantum dot layer 11 since the electron transport layer 4 in the area other than the third target area A3 is formed on the photoresist 6, the area other than the third target area A3 is not The electron transport layer 4 is peeled off, and the third quantum dot layer 91 and the electron transport layer 4 are formed only in the third target area A3.
  • the selected solvent can only The sacrificial layer is dissolved without dissolving the second quantum dot layer, so as to prevent the prepared second quantum dot layer from being lost.
  • a patterned quantum dot layer can be formed by using the methods shown in FIGS. 3A-3K or by using the methods shown in FIGS. 5A-5J.
  • FIGS. 3A to 3K are the formation of the electron transport layer 4 first and then the sacrificial layer 5 is formed.
  • FIGS. 5A to 5J are the formation of the sacrificial layer 5 first and then the subsequent formation of the electron transport layer 4.
  • the electron transport layer 4 is generally sputtered. , or coating electron transport layer material nanoparticles, sol-gel and other methods to form.
  • the materials for forming the electron transport layer 4 may be mixed to form a sol, and then spin-coated, followed by a high-temperature annealing treatment to remove the solvent to form the electron transport layer 4.
  • the temperature of the annealing treatment is higher than 180°C, and the material of the sacrificial layer 5 is not resistant to high temperature. Therefore, if the sacrificial layer 5 is formed first and then the electron transport layer 4 is formed by using FIG. 5A to FIG. 5J , the sol-gel method cannot be used to form the electron transport layer. 4, that limits the fabrication method of the electron transport layer 4, so when using the sol-gel method to prepare the electron transport layer, it is preferable to use the method of first forming the electron transport layer 4 and then forming the sacrificial layer 5 in FIGS. Quantum dot layer.
  • the color of light emitted by the first quantum dot layer, the color of light emitted by the second quantum dot layer, and the color of light emitted by the third quantum dot layer are red, green, and blue, respectively.
  • a patterned quantum dot layer is formed by means of a sacrificial layer. In the process of peeling off the sacrificial layer and the photoresist, the sacrificial layer and the photoresist can be peeled off without an ultrasonic process, and the quantum dot layer and the photoresist can be peeled off. The integrity of the transport layer, thereby improving the performance of the device.
  • the contact angle between the material of the sacrificial layer 5 and water is greater than 90°, so sacrificing
  • the material of the layer 5 is a material with strong hydrophobicity, that is, the affinity between the material of the sacrificial layer 5 and the electron transport layer 4 or the cathode 2 is low.
  • the photoresist 6 and the sacrificial layer 5 can be peeled off only by soaking or rinsing.
  • the specific material of the sacrificial layer 5 is not specifically described, but the material of the sacrificial layer 5 and the electron transport are disclosed.
  • the hydrophilic and hydrophobic properties of the layer 4 material and the cathode 2 material are opposite, because the electron transport layer 4 material is generally ZnO, and the cathode 2 material is generally metal oxide transparent conductive materials such as ITO, IGZO, AZO, etc.
  • the cathode 2 material is ITO, ZnO and The surface of ITO has a large number of hydroxyl groups, so ZnO and ITO are hydrophilic, so the hydrophobic sacrificial layer 5 material is used.
  • the material of the sacrificial layer may be a material having Si-O-Si hydrophobic chains.
  • the material of the sacrificial layer includes but is not limited to at least one of the following materials: polymethylsilsesquioxane , Methacrylamide polysilsesquioxane, polyphenylsilsesquioxane, polydimethylsiloxane, polyfluorosiloxane, polychlorosiloxane.
  • polymethylsilsesquioxane is shown in Figure 6A
  • the structural formula of methacrylamide polysilsesquioxane is shown in Figure 6B
  • the structural formula of polyphenylsilsesquioxane is shown in Figure 6C
  • These materials all include Si-O-Si hydrophobic chains, which have low affinity with the electron transport layer or cathode, and are easy to peel off the subsequent photoresist.
  • Si is a tetravalent element
  • * in Figures 6A-6C indicates that Si can also be connected with other groups, such as alkane groups, methoxy groups, ester groups, and the like.
  • the material of the sacrificial layer 5 used is the polyphenyl silsesquioxane shown in FIG. 6C .
  • the method for preparing polyphenylsilsesquioxane is as follows:
  • phenyltriethoxysilane As raw material, mix phenyltriethoxysilane, ethanol and 0.01% hydrochloric acid, and stir in a flask for more than 8 hours. First, phenyltriethoxysilane is hydrolyzed to obtain phenyl Silanol; then add 4% ammonia water and continue to stir for 24 hours. In this step, phenyl silsesquioxane is obtained by dehydration condensation of silanol bonds, and polyphenylene can be formed by polycondensation between multiple molecules under the action of ammonia water.
  • the embodiments of the present disclosure include, but are not limited to, the sacrificial layer materials of several materials with Si-O-Si hydrophobic chains listed above.
  • the main chain or branch chain of the sacrificial layer material may be a fluorine-based hydrophobic group having -F or -CF 3 .
  • the material of the sacrificial layer includes but is not limited to at least one of the following materials: fluoropolystyrene, fluoropolystyrene, fluoropolystyrene Polyacrylate.
  • fluoropolystyrene the structural formula of fluoropolystyrene is shown in Fig. 8A
  • the structural formula of fluoropolyacrylate can be shown in Fig. 8B and Fig. 8C
  • Fig. 8B has -F substituent on the main chain
  • Fig. 8C is in the branch Has a -CF 3 substituent on the chain.
  • R in FIG. 8B can be a group such as an alkane group, a methoxy group, an ester group, and the like, and R′ can be an alkane group or the like.
  • These materials all include fluorine-based hydrophobic groups, which have low affinity with the electron transport layer or the cathode, and are easy to peel off the subsequent photoresist.
  • the material of the sacrificial layer 5 used is the fluoropolyacrylate shown in FIG. 8C :
  • the method for preparing fluoropolyacrylate is as follows:
  • polyethylene glycol acrylate is obtained through esterification, as shown in FIG. 9A .
  • azobisisobutyronitrile as an initiator, polyethylene glycol acrylate and hexafluorobutyl methacrylate are polymerized to finally obtain a fluoropolyacrylate polymer, as shown in FIG. 9B .
  • the embodiments of the present disclosure include, but are not limited to, several sacrificial layer materials whose main chain or branch chain has -F or -CF 3 fluorine hydrophobic group listed above.
  • the material of the electron transport layer includes ZnO, ZnMgO, or ZnAlOx.
  • the characteristics of these electron transport layer materials are that the surface has a large number of hydroxyl groups and has strong hydrophilic properties.
  • the examples of the present disclosure are described by taking the electron transport material as hydrophilic as an example.
  • the electron transport material may also have hydrophobicity.
  • the material of the sacrificial layer can be a material with a corresponding hydrophilic property to reduce the bonding force of the interface between the two, so as to facilitate the subsequent peeling of the photoresist.
  • the embodiments of the present disclosure are described by taking a device with an inverted structure as an example.
  • the aforementioned front film layer can be a hole transport layer or an anode. Therefore, the choice of the material of the sacrificial layer only needs to be The hydrophilic and hydrophobic properties of the hole transport layer or the anode may be opposite, and the specific patterning process of the quantum dot layer is similar to the preparation method of the aforementioned inverted structure device, which will not be repeated here.
  • an embodiment of the present disclosure also provides a quantum dot light-emitting device, as shown in FIG. 10 , comprising a cathode 2 , quantum dot layers ( 81 , 91 , 11 ) and an anode 10 that are stacked in sequence, wherein the quantum dots
  • the layers (81, 91, 11) are quantum dot layers formed by the aforementioned quantum dot layer patterning method.
  • the above quantum dot light-emitting device specifically includes: a substrate 1 , a cathode 2 , an electron transport layer 4 , and a quantum dot layer arranged in sequence on the substrate 1 . ( 81 , 91 , 11 ), the hole transport layer 12 , the hole injection layer 13 , and the anode 10 .
  • the light-emitting principle of the electroluminescent device is that the holes of the anode and the electrons of the cathode are transported to the light-emitting layer (quantum dot layer) for compound light emission. It is difficult to transport electrons and holes, and the transmission rate and quantity are also very different. Therefore, in order to balance the concentrations of electrons and holes, a hole injection layer, a hole injection layer, a hole injection layer, a hole injection layer, a hole injection layer, a hole injection layer, a hole injection layer, a hole injection layer, a hole injection layer, a hole injection layer, a hole injection layer, a For the hole transport layer, an electron transport layer is arranged between the light-emitting layer (quantum dot layer) and the cathode.
  • which layers are required can be selected according to actual needs.
  • the base may include a base substrate, a driving circuit located on the base substrate, and structures such as a passivation layer and a planarization layer located above the driving circuit.
  • the embodiment of the present disclosure takes an inverted structure as an example. After the anode is fabricated, the embodiment of the present disclosure further includes a packaging process, a cutting process, and a bonding process of the quantum dot light-emitting device, all of which are It is the same as the prior art, and will not be repeated here.
  • the preparation method of the quantum dot light-emitting device includes, but is not limited to, one or more of spin coating, evaporation, chemical vapor deposition, physical vapor deposition, magnetron sputtering, and the like.
  • the cathode 2 is formed on the substrate 1, and the manufacturing method of the cathode 2 is the same as that in the prior art, and will not be described in detail here; then, an electron transport layer 4 is formed on the cathode 2;
  • the method is the same as the prior art, and will not be described in detail here; then, using the above-mentioned quantum dot layer patterning method to form a first quantum dot layer 81, a second quantum dot layer 91 and a third quantum dot layer 4 on the electron transport layer 4
  • Encapsulation is performed after the preparation of the above-mentioned film layers, and the preparation of the quantum dot light-emitting device with the inverted structure in the embodiment of the present disclosure is completed.
  • FIG. 11 in the embodiment of the present invention takes the quantum dot light-emitting device as an example of an inverted structure to illustrate the manufacturing method.
  • the quantum dot light-emitting device may also be an upright structure, as shown in FIG. 12 , when the quantum dot light-emitting device is an inverted structure.
  • the difference from the inverted structure is that the upright structure forms an anode 10, a hole injection layer 13, a hole transport layer 12, and a quantum dot layer (81, 91, 11) on the substrate 1 in sequence. ), the electron transport layer 4 and the cathode 2, which are not described in detail here.
  • the specific preparation process of the quantum dot light-emitting device with the upright structure please refer to the above-mentioned preparation method of the quantum dot light-emitting device with the inverted structure.
  • the present disclosure does not limit the light-emitting type of the quantum dot light-emitting device, such as not limited to bottom-emitting light or top-emitting light.
  • the quantum dot light-emitting device provided by the embodiments of the present disclosure further includes other functional film layers known to those skilled in the art, which will not be described in detail here.
  • an embodiment of the present disclosure further provides a display device including the above quantum dot light-emitting device provided by an embodiment of the present disclosure.
  • the display device can be any product or component with a display function, such as a mobile phone, a tablet computer, a TV, a monitor, a notebook computer, a digital photo frame, a navigator, and the like.
  • Other essential components of the display device should be understood by those of ordinary skill in the art, and will not be repeated here, nor should it be regarded as a limitation of the present disclosure.
  • the problem-solving principle of the display device is similar to that of the aforementioned quantum dot light-emitting device. Therefore, the implementation of the display device may refer to the aforementioned implementation of the quantum dot light-emitting device, and the repetition will not be repeated here.
  • the affinity between the two materials of the front film layer and the sacrificial layer can be reduced, so that the subsequent sacrificial layer and the sacrificial layer can be The peeling of the photoresist becomes easy, and the sacrificial layer and the photoresist can be peeled off without using ultrasonic waves, so as to maintain the integrity of other film layers of the device where the quantum dot layer is located, thereby improving the performance of the device.

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Abstract

一种量子点层图案化的方法，包括：在基底(1)上依次形成层叠的前膜层和牺牲层(5)；其中，牺牲层与前膜层中其中之一为亲水性，另一个为疏水性；在牺牲层上形成具有通孔的光刻胶(6)，通孔对应目标区域，在光刻胶的遮挡下刻蚀目标区域的牺牲层；覆盖量子点材料，并对目标区域的量子点材料进行固化；去除剩余的牺牲层和光刻胶，在目标区域形成图案化的量子点层。

Description

量子点层图案化的方法 技术领域
本公开涉及显示技术领域，特别涉及一种量子点层图案化的方法。
背景技术
量子点(Quantum dots，QDs)，又名半导体纳米晶、半导体纳米颗粒，是指尺寸在空间三个维度上均处于纳米数量级或由它们作为基本单元构成的纳米固体材料，是在纳米尺度上的原子和分子的集合体。基于量子点材料的发光二极管被称为量子点发光二极管(Quantum dot light-emitting diode，QLED)，是一种新型的发光器件。
发明内容
本公开实施例提供的一种量子点层图案化的方法，包括：
在基底上依次形成层叠的前膜层和牺牲层；其中，所述牺牲层与所述前膜层中其中之一为亲水性，另一个为疏水性；
在所述牺牲层上形成具有通孔的掩膜层，所述通孔对应目标区域，在所述掩膜层的遮挡下刻蚀所述目标区域的牺牲层；
覆盖量子点材料，并对所述目标区域的量子点进行固化；
去除剩余的牺牲层，在所述目标区域形成图案化的量子点层。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，在所述牺牲层上形成具有通孔的掩膜层，具体包括：
在所述牺牲层上形成光刻胶，对所述光刻胶进行构图，去除所述目标区域的光刻胶，以形成所述具有通孔的掩膜层。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述在基底上依次形成层叠的前膜层和牺牲层，具体包括：
在所述基底上形成电子传输层；其中，所述电子传输层为所述前膜层， 且所述电子传输层具有亲水性；
在所述电子传输层背离所述基底一侧形成所述牺牲层；其中，所述牺牲层具有疏水性。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述在基底上依次形成层叠的前膜层和牺牲层，具体包括：
在所述基底上形成阴极；其中，所述阴极为所述前膜层，且所述阴极具有亲水性；
在所述阴极背离所述基底一侧形成所述牺牲层；其中，所述牺牲层具有疏水性。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，在去除所述目标区域的牺牲层之后，且在覆盖量子点材料之前，还包括：
形成电子传输层。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述牺牲层的材料与水的接触角大于90°。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述牺牲层的材料具有Si-O-Si疏水链。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述牺牲层的材料包括以下至少其中之一：聚甲基倍半硅氧烷、甲基丙烯酰胺聚倍半硅氧烷、聚苯基倍半硅氧烷、聚二甲基硅氧烷、聚氟硅氧烷、聚氯硅氧烷。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述牺牲层材料的主链或者支链具有-F或者-CF 3的氟类疏水基团。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述牺牲层的材料包括以下至少其中之一：氟代聚苯乙烯、氟代聚丙烯酸酯。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，在所述掩膜层的遮挡下刻蚀所述目标区域的牺牲层，具体包括：
采用溶剂浸泡或者溶剂冲洗的方式去除剩余的牺牲层和光刻胶。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述对 所述光刻胶进行构图，去除目标区域的光刻胶，具体包括：
采用掩膜版遮挡所述光刻胶，所述掩膜版包括透光区域和遮光区域，所述透光区域对应所述光刻胶中接受光照射的保留区域，所述遮光区域对应所述目标区域；
采用溶剂去除所述目标区域的光刻胶。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述去除所述目标区域的牺牲层，具体包括：
采用氧气等离子体刻蚀掉所述目标区域的牺牲层。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述覆盖量子点材料，并对所述目标区域的量子点进行固化，具体包括：
覆盖具有光敏材料的量子点材料；
采用预设波长的光照射所述目标区域的量子点材料；其中，在所述预设波长的光照射下，所述光敏材料或所述光敏材料在所述光照射后的生成物与所述量子点表面的配体发生反应，使所述配体从所述量子点表面脱落，以改变所述目标区域量子点的溶解性，使所述目标区域的量子点发生聚沉，以固化所述目标区域的量子点；
或，
所述覆盖量子点材料，并对所述目标区域的量子点进行固化，具体包括：
覆盖表面具有可交联配体的量子点材料；
采用预设波长的光照射所述目标区域的量子点材料，使所述目标区域的量子点发生交联，以固化所述目标区域的量子点。
可选地，在本公开实施例提供的上述量子点层图案化的方法中，所述电子传输层的材料包括ZnO、ZnMgO或ZnAlOx。
附图说明
图1为本公开实施例提供的一种量子点层图案化方法的流程示意图；
图2为本公开实施例提供的又一种量子点层图案化方法的流程示意图；
图3A-图3K为本公开实施例提供的量子点层图案化方法中各制备步骤的结构示意图；
图4为本公开实施例提供的又一种量子点层图案化方法的流程示意图；
图5A-图5J为本公开实施例提供的量子点层图案化方法中各制备步骤的结构示意图；
图6A为本公开实施例提供的聚甲基倍半硅氧烷的结构示意图；
图6B为本公开实施例提供的甲基丙烯酰胺聚倍半硅氧烷的结构示意图；
图6C为本公开实施例提供的聚苯基倍半硅氧烷的结构示意图；
图7为图6C所示的结构的合成示意图；
图8A为本公开实施例提供的氟代聚苯乙烯的结构示意图；
图8B为本公开实施例提供的一种氟代聚丙烯酸酯的结构示意图；
图8C为本公开实施例提供的又一种氟代聚丙烯酸酯的结构示意图；
图9A和图9B分别为图8C所示的结构的合成示意图；
图10为本公开实施例提供的量子点发光器件的结构示意图；
图11为本公开实施例提供的倒置结构的量子点发光器件的结构示意图；
图12为本公开实施例提供的正置结构的量子点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。显然，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。并且在不冲突的情况下，本公开中的实施例及实施例中的特征可以相互组合。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他实施例，都属于本公开保护的范围。
除非另外定义，本公开使用的技术术语或者科学术语应当为本公开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“包括”或者“包含”等类似的词语意指出现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。“内”、“外”、“上”、“下”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。
需要注意的是，附图中各图形的尺寸和形状不反映真实比例，目的只是示意说明本公开内容。并且自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。
量子点的胶体溶液可以采用打印、转印、光刻等方式进行图案化，但是打印设备昂贵且分辨率有限，近年来许多研究者在光刻图案化方面做了很多工作。有采用直接光刻法来图案化量子点膜层的，即采用交联配体的方式，在紫外光照射下，量子点配体发生交联固化，非交联部分由于溶解性大而能够被溶剂洗掉，但该方式在制备全彩器件时容易由于量子点的残留而造成混色。
而采用牺牲层辅助的方式进行图案化时，在不需要的像素中，量子点可以跟随牺牲层和光刻胶一起被剥离掉，不易形成混色；但是该方法中，常用的牺牲层材料为聚乙烯吡咯烷酮，而该材料是可以溶于水和乙醇中的，具有较强的亲水性能；例如对于倒置量子点器件，制作图案化的量子点层之前，可以在电子传输层上制作牺牲层和光刻胶层，也可以在透明电极层上制作牺牲层和光刻胶层，即牺牲层与电子传输层或透明电极层直接接触，由于电子传输层和透明电极层表面通常会有羟基的存在，具有较强的亲水性能；根据相似相溶的原则，两个表面均具有相同的亲水或者疏水性能时，牺牲层与电子传输层或透明电极层表面之间的作用力就较强，使得后续光刻胶的剥离较为困难。因此在牺牲层刻蚀完，量子点沉积之后，剥胶过程通常需要采用超声辅助来加快剥离过程。在超声剥胶过程中，由于超声暴力的原因，会造成电子传输层和量子点膜层的部分脱落，降低了膜层的完整性，使器件发光不均匀。因此解决膜层之间的亲和力，提高膜层完整性对于提高器件发光性能 具有十分重要的意义。
为了解决上述剥胶过程需要采用超声辅助来加快剥离过程，造成电子传输层和量子点膜层的部分脱落，降低膜层的完整性，使器件发光不均匀的问题，本公开实施例提供的一种量子点层图案化的方法，如图1所示，包括：
S101、在基底上依次形成层叠的前膜层和牺牲层；其中，牺牲层与前膜层中其中之一为亲水性，另一个为疏水性；
S102、在所述牺牲层上形成具有通孔的掩膜层，所述通孔对应目标区域，在所述掩膜层的遮挡下刻蚀所述目标区域的牺牲层；
S103、覆盖量子点材料，并对目标区域的量子点进行固化；
S104、去除剩余的牺牲层，在目标区域形成图案化的量子点层。
本公开实施例提供的上述量子点层图案化的方法，通过选择亲疏水性相反的前膜层和牺牲层，这样可以降低前膜层和牺牲层两种材料之间的亲和力，从而使后续牺牲层和掩膜层的剥离变得容易，不需要采用超声的方式即可将牺牲层和掩膜层剥离，保持该量子点层所在器件的其它膜层的完整性，从而提升器件的性能。
在一种可能的实现方式中，在本公开实施例提供的上述量子点层图案化的方法中，覆盖量子点材料，并对目标区域的量子点进行固化，具体包括：
利用旋涂、刮涂、喷涂、喷墨打印、电喷印中的一种方式或多种方式组合覆盖量子点材料。
本领域技术人员可以理解的是，覆盖量子点材料的方式也可以不局限在上述几种方式。
在一种可能的实现方式中，在本公开实施例提供的上述量子点层图案化的方法中，在牺牲层上形成具有通孔的掩膜层，具体可以包括：
在牺牲层上形成光刻胶，对光刻胶进行构图，去除目标区域的光刻胶，以形成具有通孔的掩膜层。由于光刻胶仅需曝光显影即可形成图案化的光刻胶图形，因此可以根据需要形成的图案化量子点层的位置来图案化光刻胶，简单方便制作，因此本公开实施例采用图案化的光刻胶作为掩膜层。
当然，掩膜层也不局限于采用光刻胶形成，例如掩膜层也可是采用石英材料、金属材料制作的具有通孔区域的掩膜层。
具体地，本公开实施例采用图案化的光刻胶作为掩膜层，由于需要对光刻胶进行曝光显影形成图案化的区域，以负性光刻胶为例，曝光区域保留下来，未曝光区域被显影掉，保留下来的光刻胶由于经过曝光，会发生变性，一般需要酸或碱才能清洗掉曝光后的光刻胶，而酸碱的腐蚀性会破坏量子点性能，因此需要在光刻胶之前引入牺牲层，采用普通的溶剂就可以剥离掉牺牲层，即引入牺牲层是为了更好的剥离光刻胶，并且本公开的牺牲层与前膜层的亲疏水性能相反，因此不用超声的方式即可将牺牲层和光刻胶剥离，保持该量子点层所在器件的其它膜层的完整性，从而提升器件的性能。
本公开实施例在后续的制作方法中均采用牺牲层+光刻胶作为掩膜层的方案制作图案化的量子点层。
可选地，本公开实施例提供的量子点包括但不限于CdS、CdSe、ZnSe、InP、PbS、CsPbCl 3、CsPbBr 3、CsPhI 3、CdS/ZnS、CdSe/ZnSe、CdSe/ZnS、ZnSe、InP/ZnS、PbS/ZnS、CsPbCl 3/ZnS、CsPbBr 3/ZnS、CsPhI 3/ZnS等量子点。
目前，电致发光器件可以分为正置结构和倒置结构，正置结构和倒置结构的区别在于膜层的制作顺序不同。具体地，正置结构是在基底上依次形成阳极、空穴注入层、空穴传输层、量子点层、电子传输层和阴极，倒置结构是在基底上依次形成电子传输层、量子点层、空穴传输层、空穴注入层和阳极。
需要说明的是，本公开实施例主要以倒置结构的发光器件为例对量子点层图案化的方法进行详细说明，当然本公开实施例也适用于正置结构中量子点层图案化的方法。
为了实现全彩显示，量子点层一般包括不同颜色的图案化的量子点，本发明实施例以量子点层包括第一量子点层、第二量子点层和第三量子点层为例，结合附图详细介绍本发明实施例提供的纳米粒子层图案化的方法。
制备量子点溶液，以量子点为InP/ZnS为例，分别制备不同颜色的第一量 子点溶液、第二量子点溶液和第三量子点溶液。具体地，可以通过但不限于溶液相合成法、水热法、溶剂热法等方法形成InP/ZnS量子点。
在一种可能的实现方式中，在本公开实施例提供的上述量子点层图案化的方法中，在基底上依次形成层叠的前膜层和牺牲层，如图2所示，具体可以包括：
S201、在基底上形成电子传输层；其中，电子传输层为前膜层，且电子传输层具有亲水性；
具体地，如图3A所示，在基底1上形成阴极2，阴极2材料可以为透明金属氧化物导电材料，例如ITO(氧化铟锡)、AZO(铝掺杂的氧化锌)、IGZO(铟镓锌氧化物)等，将形成有阴极2的基底1依次用水、乙醇和丙酮清洗10分钟，之后用气枪吹干，并用紫外臭氧处理10分钟，接着，在阴极2背离基底1一侧形成像素界定层3，像素界定层3具有露出阴极2的多个像素开口；如图3B所示，在像素开口内的阴极2上形成电子传输层4，电子传输层4的材料一般为ZnO，例如在阴极2上旋涂30mg/ml的ZnO纳米粒子溶液，并在120℃下退火10分钟，ZnO表面通常会有大量羟基的存在，因此电子传输层4具有较强的亲水性能。
S202、在电子传输层背离基底一侧形成牺牲层；其中，牺牲层具有疏水性；
具体地，如图3C所示，在电子传输层4背离基底1一侧形成牺牲层5，为了降低电子传输层4和牺牲层5之间的亲和力，牺牲层5选择具有疏水性能的材料。例如，选择摩尔质量大于10 4g/mol的聚苯基倍半硅氧烷作为牺牲层材料(后续详细介绍该材料)，在摩尔质量大于10 4g/mol时，该聚合物可以溶于氯苯而不溶于二甲苯。将聚苯基倍半硅氧烷溶于氯苯中，配制成浓度为30mg/ml的溶液，并将该聚苯基倍半硅氧烷溶液旋涂到电子传输层4上，放置10分钟晾干。
接着，如图3D所示，在牺牲层5上形成光刻胶6。
接着，对光刻胶进行构图，去除目标区域的光刻胶；具体地，如图3E所 示，采用掩膜版7遮挡光刻胶6，掩膜版7包括透光区域71和遮光区域72，透光区域71对应光刻胶6中接受光照射的保留区域，遮光区域72对应制作第一量子点的第一目标区域A1；如图3F所示，采用溶剂去除第一目标区域A1的光刻胶。具体地，由于前述采用的牺牲层材料不溶于二甲苯，因此可以采用二甲苯对第一目标区域A1的光刻胶进行显影。
接着，如图3G所示，在掩膜层(光刻胶)的遮挡下刻蚀第一目标区域A1的牺牲层；具体地，可以采用氧气等离子体刻蚀掉第一目标区域A1的牺牲层。
接着，如图3H所示，在图3G的基础上覆盖第一量子点材料8，并对第一目标区域A1的第一量子点材料8进行固化。
具体地，对第一目标区域A1的第一量子点材料8进行固化，可以采用如下方式：首先覆盖具有光敏材料的第一量子点材料8，例如将光敏材料和第一量子点材料8混合后覆盖；然后采用预设波长的光(例如紫外光)照射第一目标区域A1的第一量子点材料8；其中，在预设波长的光照射下，光敏材料或光敏材料在光照射后的生成物与第一量子点表面的配体发生反应，使配体从第一量子点表面脱落，以改变第一目标区域A1第一量子点的溶解性，使第一目标区域A1的第一量子点发生聚沉，以固化第一目标区域A1的第一量子点。
进一步地，在具体实施时，在本公开实施例提供的上述量子点层图案化的方法中，光敏材料可以包括光致生酸剂、烯烃类物质或炔烃类物质。具体地，当光敏材料为光致生酸剂时，光致生酸剂在紫外光的照射下产生氢离子，氢离子与第一量子点表面的配体结合，使配体从第一量子点表面脱落，没有配体的第一量子点的溶解性与具有配体的第一量子点的溶解性不同，从而可以使第一目标区域A1内没有配体的第一量子点发生聚沉，从而固化第一目标区域A1的第一量子点。当光敏材料为烯烃类物质或炔烃类物质时，烯烃类物质和炔烃类物质可以直接与第一量子点表面的配体结合，使配体从第一量子点表面脱落，从而实现固化第一目标区域A1的第一量子点。
具体地，对第一目标区域A1的第一量子点材料8进行固化，也可以采用如下方式：首先覆盖表面具有可交联配体的第一量子点材料8，一般制备的量子点表面的配体不具有交联功能，可以采用交联试剂取代量子点表面的原始配体，从而制备得到具有可交联配体的第一量子点材料8；然后采用预设波长的光(例如紫外光)照射第一目标区域A1的第一量子点材料8，第一目标区域A1的第一量子点发生交联，形成稳固的交联网络结构，从而可以固化第一目标区域A1的第一量子点。
接着，如图3I所示，去除剩余的牺牲层5和光刻胶6，在第一目标区域A1形成图案化的第一量子点层81。由于牺牲层5和电子传输层4的亲疏水性能相反，因此牺牲层5和电子传输层4之间的亲和力较差，因此可以直接采用溶剂(由于牺牲层溶于氯苯，因此溶剂可以采用氯苯)浸泡或者溶剂(氯苯)冲洗的方式去除剩余的牺牲层5和光刻胶6，而不需要像相关技术中采用超声辅助来加快牺牲层5和光刻胶6的剥离过程，因此本公开中牺牲层5和光刻胶6的剥离更加容易，不需要采用超声的方式即可将牺牲层5和光刻胶6剥离，保持第一量子点层81和电子传输层4的完整性，从而提升器件的性能。
接着，采用图3C-图3I相同的步骤在第二目标区域A2形成第二量子点层91，如图3J所示；其中形成第二量子点层91与形成第一量子点层81的区别在于覆盖的是第二量子点材料。
最后，采用图3C-图3I相同的步骤在第二目标区域A2形成第三量子点层11，如图3K所示；其中形成第三量子点层11与形成第一量子点层81的区别在于覆盖的是第三量子点材料。
具体地，图3A-图3K所示的制作图案化的量子点层是以前膜层为电子传输层4，即以在阴极2上先形成电子传输层4，再形成牺牲层5、光刻胶6以及量子点材料为例进行说明的。
当然，在又一种可能的实现方式中，在具体实施时，在本公开实施例提供的上述量子点层图案化的方法中，在基底上依次形成层叠的前膜层和牺牲层，如图4所示，具体可以包括：
S401、在基底上形成阴极；其中，阴极为前膜层，且阴极具有亲水性；
具体地，如图3A所示，在基底1上形成阴极2，阴极2材料可以为透明金属氧化物导电材料，例如ITO(氧化铟锡)、AZO(铝掺杂的氧化锌)、IGZO(铟镓锌氧化物)等，本公开实施例以阴极2材料为ITO为例，将形成有阴极2的基底1依次用水、乙醇和丙酮清洗10分钟，之后用气枪吹干，并用紫外臭氧处理10分钟，接着，在阴极2背离基底1一侧形成像素界定层3，像素界定层3具有露出阴极2的多个像素开口，由于阴极2材料为ITO等透明导电材料，ITO表面通常会有大量羟基的存在，因此阴极2具有较强的亲水性能。
S402、在阴极背离基底一侧形成牺牲层；其中，牺牲层具有疏水性；
具体地，如图5A所示，在阴极2背离基底1一侧形成牺牲层5，为了降低阴极2和牺牲层5之间的亲和力，牺牲层5选择具有疏水性能的材料。例如，选择摩尔质量大于10 4g/mol的聚苯基倍半硅氧烷作为牺牲层材料(后续详细介绍该材料)，在摩尔质量大于10 4g/mol时，该聚合物可以溶于氯苯而不溶于二甲苯。将聚苯基倍半硅氧烷溶于氯苯中，配制成浓度为30mg/ml的溶液，并将该聚苯基倍半硅氧烷溶液旋涂在阴极2上，放置10分钟晾干。
接着，如图5B所示，在牺牲层5上形成光刻胶6。
接着，对光刻胶进行构图，去除目标区域的光刻胶；具体地，如图5C所示，采用掩膜版7遮挡光刻胶6，掩膜版7包括透光区域71和遮光区域72，透光区域71对应光刻胶6中接受光照射的保留区域，遮光区域72对应制作第一量子点的第一目标区域A1；如图5D所示，采用溶剂去除第一目标区域A1的光刻胶。具体地，由于前述采用的牺牲层材料不溶于二甲苯，因此可以采用二甲苯对第一目标区域A1的光刻胶进行显影。
接着，如图5E所示，在掩膜层(光刻胶)的遮挡下刻蚀第一目标区域A1的牺牲层；具体地，可以采用氧气等离子体刻蚀掉第一目标区域A1的牺牲层。
接着，如图5F所示，在图5E的基础上形成电子传输层4。
接着，如图5G所示，在图5F的基础上覆盖第一量子点材料8，并对第一目标区域A1的第一量子点材料8进行固化。具体地，对第一目标区域A1的第一量子点材料8进行固化的方式可以参见前述对图3H步骤描述的固化方式，在此不做赘述。
接着，如图5H所示，去除剩余的牺牲层5和光刻胶6，在第一目标区域A1形成图案化的第一量子点层81。由于牺牲层5和阴极2的亲疏水性能相反，因此牺牲层5和阴极2之间的亲和力较差，因此可以直接采用溶剂(由于牺牲层溶于氯苯，因此溶剂可以采用氯苯)浸泡或者溶剂(氯苯)冲洗的方式去除剩余的牺牲层5和光刻胶6，而不需要像相关技术中采用超声辅助来加快牺牲层5和光刻胶6的剥离过程，因此本公开中牺牲层5和光刻胶6的剥离更加容易，不需要采用超声的方式即可将牺牲层5和光刻胶6剥离，保持第一量子点层81和电子传输层4的完整性，从而提升器件的性能。
具体地，由于非第一目标区域A1以外区域的电子传输层4是形成在光刻胶6之上的，因此非第一目标区域A1以外区域的电子传输层4被剥离掉，仅在第一目标区域A1形成第一量子点层81和电子传输层4。
接着，采用图5A-图5H相同的步骤在第二目标区域A2形成第二量子点层91，如图5I所示；其中形成第二量子点层91与形成第一量子点层81的区别在于覆盖的是第二量子点材料。
具体地，在制作第二量子点层91的过程中，由于非第二目标区域A2以外区域的电子传输层4是形成在光刻胶6之上的，因此非第二目标区域A2以外区域的电子传输层4被剥离掉，仅在第二目标区域A2形成第二量子点层91和电子传输层4。
具体地，在制作第二量子点层91的过程中，由于再次形成的牺牲层会与第一量子点层接触，因此在采用溶剂剥离牺牲层和光刻胶的过程中，选择的溶剂只能溶解牺牲层而不溶解第一量子点层，以防止制作好的第一量子点层丢失。
最后，采用图5A-图5H相同的步骤在第二目标区域A2形成第三量子点 层11，如图5J所示；其中形成第三量子点层11与形成第一量子点层81的区别在于覆盖的是第三量子点材料。
具体地，在制作第三量子点层11的过程中，由于非第三目标区域A3以外区域的电子传输层4是形成在光刻胶6之上的，因此非第三目标区域A3以外区域的电子传输层4被剥离掉，仅在第三目标区域A3形成第三量子点层91和电子传输层4。
具体地，在制作第三量子点层11的过程中，由于再次形成的牺牲层会与第二量子点层接触，因此在采用溶剂剥离牺牲层和光刻胶的过程中，选择的溶剂只能溶解牺牲层而不溶解第二量子点层，以防止制作好的第二量子点层丢失。
因此采用图3A-图3K或采用图5A-图5J所示的方式均能形成图案化的量子点层。
需要说明的是，图3A-图3K是先形成电子传输层4再形成牺牲层5，图5A-图5J是先形成牺牲层5再后续形成电子传输层4，电子传输层4一般采用溅射，或者涂覆电子传输层材料纳米粒子、溶胶凝胶等方法形成。当使用溶胶凝胶法制备电子传输层时，可以将用于形成电子传输层4的材料混合形成溶胶，然后旋涂，旋涂之后采用高温退火处理以除去溶剂以形成电子传输层4，由于高温退火处理的温度高于180℃，而牺牲层5材料不耐高温，因此若采用图5A-图5J先形成牺牲层5再后续形成电子传输层4，则无法使用溶胶凝胶法形成电子传输层4，即限制了电子传输层4的制作方法，因此当使用溶胶凝胶法制备电子传输层时，优选采用图3A-图3K先形成电子传输层4再形成牺牲层5的方法制作图案化的量子点层。
在具体实施时，本公开实施例中第一量子点层发射的光的颜色、第二量子点层发射的光的颜色、第三量子点层发射的光的颜色分别为红色、绿色、蓝色，这样本发明实施例通过以上图案化的方法完成了全彩量子点的图案化过程。本发明实施例采用牺牲层辅助的方式形成图案化的量子点层，在剥离牺牲层和光刻胶的过程中不需要超声工艺即可将牺牲层和光刻胶剥离，保持 量子点层和电子传输层的完整性，从而提升器件的性能。
进一步地，在具体实施时，在本公开实施例提供的上述量子点层图案化的方法中，如图3C和图5A所示，牺牲层5的材料与水的接触角大于90°，这样牺牲层5材料为强疏水性的材料，即该牺牲层5材料与电子传输层4或阴极2之间的亲和力较低，在后续光刻胶和牺牲层剥离过程中，不需要采用超声工艺，而只需采用浸泡或者冲洗的方式即可剥离掉光刻胶6和牺牲层5。
具体地，前述采用图3A-图3K或采用图5A-图5J所示的方式形成图案化的量子点层时，没有具体介绍牺牲层5的具体材料，只是公开了牺牲层5材料与电子传输层4材料和阴极2材料的亲疏水性能相反，由于电子传输层4材料一般为ZnO，阴极2材料一般为ITO、IGZO、AZO等金属氧化物透明导电材料，例如阴极2材料为ITO，ZnO和ITO表面均具有大量的羟基，因此ZnO和ITO具有亲水性，因此采用疏水性的牺牲层5材料。
进一步地，在具体实施时，在本公开实施例提供的上述量子点层图案化的方法中，牺牲层的材料可以为具有Si-O-Si疏水链的材料。
进一步地，在具体实施时，在本公开实施例提供的上述量子点层图案化的方法中，牺牲层的材料包括但不限于以下材料中的至少其中之一：聚甲基倍半硅氧烷、甲基丙烯酰胺聚倍半硅氧烷、聚苯基倍半硅氧烷、聚二甲基硅氧烷、聚氟硅氧烷、聚氯硅氧烷。例如，聚甲基倍半硅氧烷的结构式如图6A所示，甲基丙烯酰胺聚倍半硅氧烷的结构式如图6B所示，聚苯基倍半硅氧烷的结构式如图6C所示；这些材料均包括Si-O-Si疏水链，与电子传输层或阴极之间的亲和力较低，易于后续光刻胶的剥离。
需要说明的是，由于Si是四价元素，图6A-图6C中的*表示Si还可以与其他基团连接，例如烷烃类基团、甲氧基、酯基等。
具体地，以前述采用图3A-图3K或采用图5A-图5J所示的方式形成图案化的量子点层时，采用的牺牲层5的材料为图6C所示的聚苯基倍半硅氧烷为例，制备聚苯基倍半硅氧烷的方法如下：
以苯基三乙氧基硅烷为原料，将苯基三乙氧基硅烷，乙醇和0.01％的盐酸 混合，在烧瓶中搅拌8小时以上，苯基三乙氧基硅烷首先通过水解反应得到苯基硅醇；之后加入4％的氨水继续搅拌24小时，这一步中通过硅醇键的脱水缩合得到苯基倍半硅氧烷，在氨水的作用下多个分子之间缩聚即可形成聚苯基倍半硅氧烷聚合物，离心分离出聚苯基倍半硅氧烷并用水洗掉多余的离子，之后烘干备用。聚苯基倍半硅氧烷的合成过程示意图如图7所示。
需要说明的是，本公开实施例包括但不限于上述列举的几种具有Si-O-Si疏水链的材料的牺牲层材料。
进一步地，在具体实施时，在本公开实施例提供的上述量子点层图案化的方法中，牺牲层材料的主链或者支链可以为具有-F或者-CF 3的氟类疏水基团。
进一步地，在具体实施时，在本公开实施例提供的上述量子点层图案化的方法中，牺牲层的材料包括但不限于以下材料中的至少其中之一：氟代聚苯乙烯、氟代聚丙烯酸酯。例如，氟代聚苯乙烯的结构式如图8A所示，氟代聚丙烯酸酯的结构式可以如图8B和图8C所示，图8B为在主链上具有-F取代基，图8C为在支链上具有-CF 3取代基。另外，图8B中的R可以为烷烃类基团、甲氧基、酯基等基团，R’可以为烷烃类基团等。这些材料均包括氟类疏水基团，与电子传输层或阴极之间的亲和力较低，易于后续光刻胶的剥离。
需要说明的是，由于Si是四价元素，图8A-图8C中的*表示C还可以与其他基团连接，例如烷烃类基团、甲氧基、酯基等。
具体地，以前述采用图3A-图3K或采用图5A-图5J所示的方式形成图案化的量子点层时，采用的牺牲层5的材料为图8C所示的氟代聚丙烯酸酯为例，制备氟代聚丙烯酸酯的方法如下：
以苯磺酸为催化剂，丙烯酸和聚乙二醇为反应原料，通过酯化反应得到聚乙二醇丙烯酸酯，如图9A所示。以偶氮二异丁腈为引发剂，将聚乙二醇丙烯酸酯与甲基丙烯酸六氟丁酯进行聚合，最终得到氟代聚丙烯酸酯聚合物，如图9B所示。
需要说明的是，本公开实施例包括但不限于上述列举的几种主链或者支 链具有-F或者-CF 3的氟类疏水基团的牺牲层材料。
进一步地，在具体实施时，在本公开实施例提供的上述量子点层图案化的方法中，电子传输层的材料包括ZnO、ZnMgO或ZnAlOx。这些电子传输层材料的特点是：表面具有大量的羟基，具有较强的亲水性能。
需要说明的是，本公开实施例是以电子传输材料为亲水性为例进行说明的，当然，在具体实施时，电子传输材料也可能具有疏水性，针对采用具有疏水性能的电子传输材料制备器件时，前述牺牲层的材料可以采用与之相对应的具有亲水性能的材料，来减小二者界面的结合力，以便后续光刻胶的剥离。
需要说明的是，本公开实施例是以倒置结构的器件为例进行说明的，当采用正置结构时，前述的前膜层就可以是空穴传输层或阳极，因此牺牲层材料的选择只要与空穴传输层或阳极的亲疏水性能相反即可，具体的量子点层图案化的工艺与前述倒置结构器件的制备方法类似，在此不做赘述。
基于同一发明构思，本公开实施例还提供了一种量子点发光器件，如图10所示，包括依次层叠设置的阴极2、量子点层(81、91、11)和阳极10，其中量子点层(81、91、11)为采用前述量子点层图案化的方法形成的量子点层。
在具体实施时，在本公开实施例提供的上述量子点发光器件中，如图11所示，具体包括：基底1，位于基底1上依次层叠设置的阴极2、电子传输层4、量子点层(81、91、11)、空穴传输层12、空穴注入层13和阳极10。
需要说明的是，电致发光器件发光的原理是：阳极的空穴和阴极的电子传输至发光层(量子点层)复合发光，由于阳极和发光层以及阴极和发光层之间能级势垒的差别，电子和空穴传输较难且传输速率和数量也大不相同，因此为了平衡电子和空穴的浓度，一般会在发光层(量子点层)与阳极之间设置空穴注入层、空穴传输层，在发光层(量子点层)与阴极之间设置电子传输层，当然，在具体实施时，可以根据实际需要进行选择需要哪几层。
具体地，本公开实施例提供的基底可以包括衬底基板、位于衬底基板上 的驱动电路以及位于驱动电路上方的钝化层、平坦层等结构。
在具体实施时，本公开实施例是以倒置结构为例，本公开实施例在制作完成阳极后，还包括量子点发光器件的封装过程、切割过程，以及绑定(bonding)过程，这些过程均与现有技术相同，在此不做赘述。
下面通过具体实施例对本公开实施例提供的量子点发光器件为倒置结构时的制备方法进行简单说明。具体地，量子点发光器件中各膜层的制备方法包括但不限于旋涂法、蒸镀法、化学气相沉积法、物理气相沉积法、磁控溅射法等中的一种或多种。
如图11所示，在基底1上形成阴极2，阴极2的制作方法与现有技术相同，在此不做详述；接着，在阴极2上形成电子传输层4；电子传输层4的制作方法与现有技术相同，在此不做详述；接着，利用上述量子点层图案化的方法在电子传输层4上形成包括第一量子点层81、第二量子点层91和第三量子点层11的量子点层；之后，在量子点层上依次制作空穴传输层12、空穴注入层13和阳极10；空穴传输层12、空穴注入层13和阳极10的制作做法与现有技术相同，在此不做详述。
在上述各膜层制备结束之后进行封装，完成本公开实施例中倒置结构的量子点发光器件的制备。
需要说明的是，本发明实施例图11是以量子点发光器件为倒置结构为例进行说明其制作方法的，当然，量子点发光器件也可以为正置结构，如图12所示，当量子点发光器件为正置结构时，与倒置结构制作的区别在于，正置结构在基底1上依次形成阳极10、空穴注入层13、空穴传输层12、量子点层(81、91、11)、电子传输层4和阴极2，在此不做详述。具体地，正置结构的量子点发光器件的具体制备流程可以参见上述倒置结构的量子点发光器件的制备方法，仅是各膜层的制备顺序发生改变，在此不做详述。
本公开对量子点发光器件的发光类型不做限制，如不限于底出光或顶出光。
具体实施时，本公开实施例提供的量子点发光器件还包括本领域技术人 员熟知的其它功能膜层，在此不做详述。
基于同一公开构思，本公开实施例还提供了一种显示装置，包括本公开实施例提供的上述量子点发光器件。该显示装置可以为：手机、平板电脑、电视机、显示器、笔记本电脑、数码相框、导航仪等任何具有显示功能的产品或部件。对于该显示装置的其它必不可少的组成部分均为本领域的普通技术人员应该理解具有的，在此不做赘述，也不应作为对本公开的限制。该显示装置解决问题的原理与前述量子点发光器件相似，因此该显示装置的实施可以参见前述量子点发光器件的实施，重复之处在此不再赘述。
本公开实施例提供的量子点层图案化的方法，通过选择亲疏水性相反的前膜层和牺牲层，这样可以降低前膜层和牺牲层两种材料之间的亲和力，从而使后续牺牲层和光刻胶的剥离变得容易，不需要采用超声的方式即可将牺牲层和光刻胶剥离，保持该量子点层所在器件的其它膜层的完整性，从而提升器件的性能。
尽管已描述了本公开的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例作出另外的变更和修改。所以，所附权利要求意欲解释为包括优选实施例以及落入本公开范围的所有变更和修改。
显然，本领域的技术人员可以对本公开实施例进行各种改动和变型而不脱离本公开实施例的精神和范围。这样，倘若本公开实施例的这些修改和变型属于本公开权利要求及其等同技术的范围之内，则本公开也意图包含这些改动和变型在内。

Claims (15)

  1. 一种量子点层图案化的方法，其中，包括：
    在基底上依次形成层叠的前膜层和牺牲层；其中，所述牺牲层与所述前膜层中其中之一为亲水性，另一个为疏水性；
    在所述牺牲层上形成具有通孔的掩膜层，所述通孔对应目标区域，在所述掩膜层的遮挡下刻蚀所述目标区域的牺牲层；
    覆盖量子点材料，并对所述目标区域的量子点进行固化；
    去除剩余的牺牲层，在所述目标区域形成图案化的量子点层。
  2. 如权利要求1所述的量子点层图案化的方法，其中，在所述牺牲层上形成具有通孔的掩膜层，具体包括：
    在所述牺牲层上形成光刻胶，对所述光刻胶进行构图，去除所述目标区域的光刻胶，以形成所述具有通孔的掩膜层。
  3. 如权利要求1所述的量子点层图案化的方法，其中，所述在基底上依次形成层叠的前膜层和牺牲层，具体包括：
    在所述基底上形成电子传输层；其中，所述电子传输层为所述前膜层，且所述电子传输层具有亲水性；
    在所述电子传输层背离所述基底一侧形成所述牺牲层；其中，所述牺牲层具有疏水性。
  4. 如权利要求1所述的量子点层图案化的方法，其中，所述在基底上依次形成层叠的前膜层和牺牲层，具体包括：
    在所述基底上形成阴极；其中，所述阴极为所述前膜层，且所述阴极具有亲水性；
    在所述阴极背离所述基底一侧形成所述牺牲层；其中，所述牺牲层具有疏水性。
  5. 如权利要求4所述的量子点层图案化的方法，其中，在去除所述目标区域的牺牲层之后，且在覆盖量子点材料之前，还包括：
    形成电子传输层。
  6. 如权利要求3-5任一项所述的量子点层图案化的方法，其中，所述牺牲层的材料与水的接触角大于90°。
  7. 如权利要求6所述的量子点层图案化的方法，其中，所述牺牲层的材料具有Si-O-Si疏水链。
  8. 如权利要求7所述的量子点层图案化的方法，其中，所述牺牲层的材料包括以下至少其中之一：聚甲基倍半硅氧烷、甲基丙烯酰胺聚倍半硅氧烷、聚苯基倍半硅氧烷、聚二甲基硅氧烷、聚氟硅氧烷、聚氯硅氧烷。
  9. 如权利要求6所述的量子点层图案化的方法，其中，所述牺牲层材料的主链或者支链具有-F或者-CF 3的氟类疏水基团。
  10. 如权利要求9所述的量子点层图案化的方法，其中，所述牺牲层的材料包括以下至少其中之一：氟代聚苯乙烯、氟代聚丙烯酸酯。
  11. 如权利要求1所述的量子点层图案化的方法，其中，所述去除剩余的牺牲层，具体包括：
    采用溶剂浸泡或者溶剂冲洗的方式去除剩余的牺牲层。
  12. 如权利要求2所述的量子点层图案化的方法，其中，对所述光刻胶进行构图，去除目标区域的光刻胶，具体包括：
    采用掩膜版遮挡所述光刻胶，所述掩膜版包括透光区域和遮光区域，所述透光区域对应所述光刻胶中接受光照射的保留区域，所述遮光区域对应所述目标区域；
    采用溶剂去除所述目标区域的光刻胶。
  13. 如权利要求1所述的量子点层图案化的方法，其中，在所述掩膜层的遮挡下刻蚀所述目标区域的牺牲层，具体包括：
    采用氧气等离子体刻蚀掉所述目标区域的牺牲层。
  14. 如权利要求1所述的量子点层图案化的方法，其中，所述覆盖量子点材料，并对所述目标区域的量子点进行固化，具体包括：
    覆盖具有光敏材料的量子点材料；
    采用预设波长的光照射所述目标区域的量子点材料；其中，在所述预设波长的光照射下，所述光敏材料或所述光敏材料在所述光照射后的生成物与所述量子点表面的配体发生反应，使所述配体从所述量子点表面脱落，以改变所述目标区域量子点的溶解性，使所述目标区域的量子点发生聚沉，以固化所述目标区域的量子点；
    或，
    所述覆盖量子点材料，并对所述目标区域的量子点进行固化，具体包括：
    覆盖表面具有可交联配体的量子点材料；
    采用预设波长的光照射所述目标区域的量子点材料，使所述目标区域的量子点发生交联，以固化所述目标区域的量子点。
  15. 如权利要求3或5所述的量子点层图案化的方法，其中，所述电子传输层的材料包括ZnO、ZnMgO或ZnAlOx。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100859282B1 (ko) * 2007-05-30 2008-09-19 전남대학교산학협력단 다중파장 발광다이오드 및 이의 제조방법
KR20110120257A (ko) * 2009-08-24 2011-11-03 한국기초과학지원연구원 양자점 형성방법
CN105449111A (zh) * 2016-01-08 2016-03-30 京东方科技集团股份有限公司 具有结合层的量子点发光二极管基板及其制备方法
CN107068607A (zh) * 2017-04-24 2017-08-18 西安电子科技大学 基于牺牲层的电极材料转移方法
CN111146325A (zh) * 2018-11-05 2020-05-12 三星电子株式会社 发光器件封装件和使用该发光器件封装件的显示装置
CN111883572A (zh) * 2020-08-06 2020-11-03 京东方科技集团股份有限公司 一种显示基板的制备方法、显示基板及显示装置
CN111900269A (zh) * 2020-07-15 2020-11-06 京东方科技集团股份有限公司 一种量子点层图案化的方法及量子点发光器件的制作方法
CN112002744A (zh) * 2020-08-13 2020-11-27 深圳市华星光电半导体显示技术有限公司 一种显示面板及其制作方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100859282B1 (ko) * 2007-05-30 2008-09-19 전남대학교산학협력단 다중파장 발광다이오드 및 이의 제조방법
KR20110120257A (ko) * 2009-08-24 2011-11-03 한국기초과학지원연구원 양자점 형성방법
CN105449111A (zh) * 2016-01-08 2016-03-30 京东方科技集团股份有限公司 具有结合层的量子点发光二极管基板及其制备方法
CN107068607A (zh) * 2017-04-24 2017-08-18 西安电子科技大学 基于牺牲层的电极材料转移方法
CN111146325A (zh) * 2018-11-05 2020-05-12 三星电子株式会社 发光器件封装件和使用该发光器件封装件的显示装置
CN111900269A (zh) * 2020-07-15 2020-11-06 京东方科技集团股份有限公司 一种量子点层图案化的方法及量子点发光器件的制作方法
CN111883572A (zh) * 2020-08-06 2020-11-03 京东方科技集团股份有限公司 一种显示基板的制备方法、显示基板及显示装置
CN112002744A (zh) * 2020-08-13 2020-11-27 深圳市华星光电半导体显示技术有限公司 一种显示面板及其制作方法

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