WO2017190378A1 - 量子点发光二极管显示器的制作方法及量子点发光二极管显示器 - Google Patents

量子点发光二极管显示器的制作方法及量子点发光二极管显示器 Download PDF

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WO2017190378A1
WO2017190378A1 PCT/CN2016/083061 CN2016083061W WO2017190378A1 WO 2017190378 A1 WO2017190378 A1 WO 2017190378A1 CN 2016083061 W CN2016083061 W CN 2016083061W WO 2017190378 A1 WO2017190378 A1 WO 2017190378A1
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quantum dot
layer
compound
dot film
emitting diode
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French (fr)
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李冬泽
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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    • 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
    • H10K59/30—Devices specially adapted for multicolour light emission
    • H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H10K50/156—Hole transporting layers comprising a multilayered structure
    • 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
    • H10K50/166—Electron transporting layers comprising a multilayered structure
    • 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
    • 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
    • H10K59/122—Pixel-defining structures or layers, e.g. banks
    • 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

Definitions

  • the present invention relates to the field of display technologies, and in particular, to a method for fabricating a quantum dot light emitting diode display and a quantum dot light emitting diode display.
  • An OLED (Organic Light-Emitting Diode) display also known as an organic electroluminescent display, is an emerging flat panel display device because of its simple preparation process, low cost, low power consumption, and high luminance.
  • the working temperature has wide adaptability, light volume, fast response, easy to realize color display and large screen display, easy to realize integration with integrated circuit driver, easy to realize flexible display, and the like, and thus has broad application prospects.
  • Quantum Dot Quantum Dot
  • Quantum dot luminescent materials have the advantages of concentrated luminescence spectrum and high color purity. In recent years, many luminescent dot-emitting materials have been reported. Quantum Dot Light-Emitting Diodes with quantum dot materials as luminescent layers (Quantum Dot Light-Emitting Diode) , QLED) device efficiency has reached 20%, I believe that with the further development of device structure design and device fabrication technology, this technical index will be greatly improved, QLED technology is also known as a new generation of display technology compared to OLED display technology.
  • the prior art uses a high-quality quantum dot material which has been prepared, and is mixed with a solvent to prepare a quantum dot film by solution film formation, due to the size and surface properties of the quantum dot material.
  • Particularity, which directly leads to film formation, is generally unsatisfactory, directly affecting device efficiency.
  • the object of the present invention is to provide a method for fabricating a quantum dot light emitting diode display, which has easy adjustment of process parameters, simple process, and material cost reduction.
  • the present invention provides a method for fabricating a quantum dot light emitting diode display, comprising the following steps:
  • Step 1 providing a substrate, forming a plurality of spaced anodes on the substrate; forming pixel defining layers on the plurality of anodes and substrates, wherein the pixel defining layers are respectively provided with numbers corresponding to the plurality of anodes Through hole
  • Step 2 sequentially forming a hole injection layer disposed above the anode and a hole transport layer disposed above the hole injection layer in each of the through holes;
  • Step 3 providing a metal complex solution, wherein the metal complex solution is a solution obtained by dispersing a metal complex M-(XCH 2 COO - H 3 N + CH 2 CH 2 OH) 2 in a non-polar solvent, wherein M includes at least one of a Cd element and a Zn element, and X includes at least one of an S element or a Se element;
  • Step 4 injecting a metal complex solution on the hole transport layer in each through hole, heating and drying to obtain a quantum dot film, the quantum dot film constituting the light emitting layer;
  • Step 5 Prepare an electron transport layer on the light-emitting layer in each of the via holes, and form a cathode over the plurality of electron transport layers and the pixel definition layer among the plurality of via holes.
  • the method for preparing the metal complex solution comprises the following steps:
  • Step 31 dissolving mercaptopropionic acid or selenopropionic acid, ethanolamine, and metal oxide or metal hydroxide in dimethoxyethanol, and heating at 50 ° C to 65 ° C until all solid materials are completely dissolved.
  • the reaction solution was obtained, and the reaction formula was as follows:
  • M includes at least one of a Cd element and a Zn element
  • X includes at least one of an S element or a Se element
  • Step 32 The reaction solution obtained in the step 31 is centrifuged, and the obtained precipitate is a metal complex M-(XCH 2 COO - H 3 N + CH 2 CH 2 OH) 2 , and the metal complex M-(XCH) 2 COO - H 3 N + CH 2 CH 2 OH) 2 is redispersed in a non-polar solvent to obtain a metal complex solution.
  • each 1 mol of metal oxide or metal hydroxide corresponds to 1 mL to 3 mL of ethanolamine, 0.6 mL to 1.8 mL of mercaptopropionic acid or selenopropionic acid, and 1 mL to 10 mL of solvent dimethoxyethanol, wherein ethanolamine
  • the volume ratio to mercaptopropionic acid or selenopropionic acid is 1:0.6;
  • the non-polar solvent includes one or more of toluene, chloroform, and n-hexane.
  • the anode is prepared by depositing a conductive layer on the substrate, and patterning the conductive layer by a photolithography process to form a plurality of anodes;
  • the method for preparing the pixel defining layer is: coating an organic photoresist material on the substrate and the plurality of anodes to form a photoresist layer, and exposing and developing the photoresist layer by using a photomask, corresponding to the number A plurality of through holes are formed over the anode to obtain a pixel defining layer.
  • the hole injection layer and the hole transport layer are all prepared by inkjet printing
  • the electron transport layer is prepared by an inkjet printing method, and the cathode is prepared by an evaporation method.
  • the quantum dot film comprises a red quantum dot film, a blue quantum dot film, and a green quantum dot film; the red quantum dot film has a light emission range of 630 nm to 690 nm, and the green quantum dot film has a light emission range of 500 nm to 560 nm.
  • the blue quantum dot film has a light emission range of 420 nm to 480 nm;
  • the red quantum dot film, the blue quantum dot film, and the green quantum dot film have the same drying temperature.
  • the material of the anode is a transparent conductive metal oxide
  • the material of the pixel defining layer is an organic photoresist material
  • the material of the hole injection layer includes a polyparaphenylene vinyl compound, a polythiophene compound, a polysilane compound, a triphenylmethane compound, a triarylamine compound, an anthraquinone compound, a pyrazoline compound, and a chewazole.
  • a compound, a carbazole compound, and a butadiene compound One or more of a compound, a carbazole compound, and a butadiene compound;
  • the material of the hole transport layer is an organic material or an inorganic material;
  • the organic material includes 4,4'-N, N'-dicarbazole-biphenyl, N'-diphenyl-N, N'-di (1-naphthyl)-1,1'-biphenyl-4,4"-diamine, 4,4',4"-tris(N-oxazolyl)-triphenylamine, and N,N'-di
  • the inorganic material includes one of NiO, and MoO 3 Or two;
  • the material of the electron transport layer is an organic material or an inorganic material;
  • the inorganic material includes one or more of ZnO, TiO 2 , WO 3 , and SnO 2 ;
  • the organic material includes 1 , 3 , 5 - 3 One of (N-phenylbenzimidazol-2-yl)benzene and 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole Species or more;
  • the material of the cathode includes one or more of aluminum, silver, and magnesium silver alloy.
  • the present invention also provides a quantum dot light emitting diode display comprising a substrate, a plurality of anodes disposed on the substrate and spaced apart from each other, and a pixel defining layer disposed on the plurality of anodes and the substrate, the pixel defining layer There are several through holes corresponding to a plurality of anodes, respectively, in each through hole a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer are sequentially disposed from bottom to top; and further includes a plurality of electron transport layers located in the plurality of through holes and a cathode above the pixel definition layer;
  • the luminescent layer is a quantum dot film formed by forming a metal complex solution, and the metal complex solution is a metal complex M-(XCH 2 COO - H 3 N + CH 2 CH 2 OH) 2 dispersed in the non- A solution obtained in a polar solvent, wherein M includes at least one of a Cd element and a Zn element, and X includes at least one of an S element or a Se element.
  • the quantum dot film comprises a red quantum dot film, a blue quantum dot film, and a green quantum dot film; the red quantum dot film has a light emission range of 630 nm to 690 nm, and the green quantum dot film has a light emission range of 500 nm to 560 nm.
  • the blue quantum dot film has a light emission range of 420 nm to 480 nm.
  • the non-polar solvent includes one or more of toluene, chloroform, and n-hexane.
  • the material of the anode is a transparent conductive metal oxide
  • the material of the pixel defining layer is an organic photoresist material
  • the material of the hole injection layer includes a polyparaphenylene vinyl compound, a polythiophene compound, a polysilane compound, a triphenylmethane compound, a triarylamine compound, an anthraquinone compound, a pyrazoline compound, and a chewazole.
  • a compound, a carbazole compound, and a butadiene compound One or more of a compound, a carbazole compound, and a butadiene compound;
  • the material of the hole transport layer is an organic material or an inorganic material;
  • the organic material includes 4,4'-N, N'-dicarbazole-biphenyl, N'-diphenyl-N, N'-di (1-naphthyl)-1,1'-biphenyl-4,4"-diamine, 4,4',4"-tris(N-oxazolyl)-triphenylamine, and N,N'-di
  • the inorganic material includes one of NiO and MoO 3 or Multiple
  • the material of the electron transport layer is an organic material or an inorganic material;
  • the inorganic material includes one or more of ZnO, TiO 2 , WO 3 , and SnO 2 ;
  • the organic material includes 1 , 3 , 5 - 3 One of (N-phenylbenzimidazol-2-yl)benzene and 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole Species or two;
  • the material of the cathode includes one or more of aluminum, silver, and magnesium silver alloy.
  • the invention also provides a method for manufacturing a quantum dot light emitting diode display, comprising the following steps:
  • Step 1 providing a substrate, forming a plurality of spaced anodes on the substrate; forming pixel defining layers on the plurality of anodes and substrates, wherein the pixel defining layers are respectively provided with numbers corresponding to the plurality of anodes Through hole
  • Step 2 sequentially forming a hole injection layer disposed above the anode and a hole transport layer disposed above the hole injection layer in each of the through holes;
  • Step 3 providing a metal complex solution, wherein the metal complex solution is a solution obtained by dispersing a metal complex M-(XCH 2 COO - H 3 N + CH 2 CH 2 OH) 2 in a non-polar solvent, wherein M includes at least one of a Cd element and a Zn element, and X includes at least one of an S element or a Se element;
  • Step 4 injecting a metal complex solution on the hole transport layer in each through hole, heating and drying to obtain a quantum dot film, the quantum dot film constituting the light emitting layer;
  • Step 5 preparing an electron transport layer on the light-emitting layer in each of the via holes, forming a cathode over the plurality of electron transport layers and the pixel definition layer of the plurality of via holes;
  • the preparation method of the metal complex solution comprises the following steps:
  • Step 31 dissolving mercaptopropionic acid or selenopropionic acid, ethanolamine, and metal oxide or metal hydroxide in dimethoxyethanol, and heating at 50 ° C to 65 ° C until all solid materials are completely dissolved.
  • the reaction solution was obtained, and the reaction formula was as follows:
  • M includes at least one of a Cd element and a Zn element
  • X includes at least one of an S element or a Se element
  • Step 32 The reaction solution obtained in the step 31 is centrifuged, and the obtained precipitate is a metal complex M-(XCH 2 COO - H 3 N + CH 2 CH 2 OH) 2 , and the metal complex M-(XCH) 2 COO - H 3 N + CH 2 CH 2 OH) 2 redispersed in a non-polar solvent to obtain a metal complex solution;
  • the anode is prepared by depositing a conductive layer on the substrate, and patterning the conductive layer by a photolithography process to form a plurality of anodes;
  • the method for preparing the pixel defining layer is: coating an organic photoresist material on the substrate and the plurality of anodes to form a photoresist layer, and exposing and developing the photoresist layer by using a photomask, corresponding to the number Forming a plurality of through holes above the anode to obtain a pixel defining layer;
  • the hole injection layer and the hole transport layer are all prepared by inkjet printing
  • the electron transport layer is prepared by an inkjet printing method, and the cathode is prepared by an evaporation method.
  • the invention has the beneficial effects that the quantum dot light-emitting diode display provided by the invention adopts a quantum dot film prepared by a metal complex solution through a film forming method to form a light-emitting layer, and the existing inkjet using quantum dot ink.
  • the process parameters are easy to adjust.
  • the art process is simple, the material cost is reduced, and the sub-pixel level precise control of the inkjet printing technology is adopted to realize the regulation of the three primary colors of R, G and B, and the color film structure is not needed, thereby realizing a lighter and thin industrial design concept.
  • the quantum dot light-emitting diode display provided by the invention adopts a quantum dot film to form a light-emitting layer, so that the quantum dot light-emitting diode display has excellent display quality, simple process and low production cost.
  • FIG. 1 is a flow chart of a method of fabricating a quantum dot light emitting diode display of the present invention
  • FIGS. 2-5 are schematic diagrams showing the first step of the method for fabricating the quantum dot light emitting diode display of the present invention.
  • step 2 is a schematic diagram of step 2 of a method for fabricating a quantum dot light emitting diode display of the present invention
  • step 4 is a schematic diagram of step 4 of a method for fabricating a quantum dot light emitting diode display of the present invention.
  • FIG. 8 is a schematic view showing the step 5 of the method for fabricating the quantum dot light emitting diode display of the present invention and the structure of the quantum dot light emitting diode display of the present invention.
  • the present invention first provides a method for fabricating a quantum dot light emitting diode display, comprising the following steps:
  • Step 1 as shown in FIG. 2-5, a substrate 10 is provided, and a plurality of spaced anodes 20 are formed on the substrate 10; a pixel defining layer (Bank) 30 is formed on the plurality of anodes 20 and 10 The pixel defining layer 30 is provided with a plurality of through holes 31 respectively corresponding to the plurality of anodes 20.
  • the method for preparing the plurality of anodes 20 is as follows: depositing a conductive layer 15 on the substrate 10 as shown in FIG. 2-3, and patterning the conductive layer 15 by using a photolithography process to form a number One anode 20.
  • the substrate 10 is a transparent substrate, preferably a glass substrate.
  • the material of the anode 20 is a transparent conductive metal oxide, preferably indium tin oxide (ITO).
  • ITO indium tin oxide
  • the method for preparing the pixel defining layer 30 is as follows: as shown in FIG. 4-5, an organic photoresist material is coated on the substrate 10 and the plurality of anodes 20 to form a photoresist layer 25, and a light is used.
  • the mask performs patterning on the photoresist layer 25, and a plurality of via holes 31 are formed corresponding to the plurality of anodes 20, respectively, to obtain a pixel defining layer 30.
  • the material of the pixel defining layer 30 is a black organic photoresist material.
  • Step 2 as shown in FIG. 6, a hole injection layer (HIL) 40 disposed above the anode 20 and a hole transport layer disposed above the hole injection layer 40 are sequentially formed in each of the via holes 31.
  • Layer (HTL) 50 Layer (HTL) 50.
  • the material of the hole injection layer 40 includes a polyparaphenylene vinylene (PPV) compound, a polythiophene compound, a polysilane compound, a triphenylmethane compound, a triarylamine compound, an anthraquinone compound, and a pyrene.
  • PSV polyparaphenylene vinylene
  • a polythiophene compound a polythiophene compound
  • a polysilane compound a triphenylmethane compound
  • a triarylamine compound an anthraquinone compound
  • pyrene a pyrene.
  • the material of the hole transport layer 50 is an organic material or an inorganic material;
  • the organic material includes 4,4'-N, N'-dicarbazole-biphenyl (CBP), N'-diphenyl group.
  • CBP 4,4'-N, N'-dicarbazole-biphenyl
  • a-NPD 4,4'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine
  • a-NPD 4,4',4"-tris(N-azolyl) a compound of triphenylamine (TCCA) and N,N'-bis[4-(N,N'-diphenyl-amino)phenyl]-N,N'-diphenylbenzidine (DNTPD) Or a plurality of;
  • the inorganic material includes one or more of NiO, and MoO 3 .
  • the hole injection layer 40 and the hole transport layer 50 are all prepared by an Ink Jet Printer (IJP) method.
  • IJP Ink Jet Printer
  • Step 3 providing a metal complex solution, wherein the metal complex solution is a solution obtained by dispersing a metal complex M-(XCH 2 COO - H 3 N + CH 2 CH 2 OH) 2 in a non-polar solvent, wherein M includes at least one of a Cd element and a Zn element, and X includes at least one of an S element or a Se element.
  • M includes at least one of a Cd element and a Zn element
  • X includes at least one of an S element or a Se element.
  • the method for preparing the metal complex solution includes the following steps:
  • Step 31 adding mercaptopropionic acid (HSCH 2 COOH) or selenopropionic acid (HSeCH 2 COOH), ethanolamine (H 2 NCH 2 CH 2 OH), and metal oxide (MO) or metal hydroxide (M (OH) 2 ) Dissolved in dimethoxyethanol, heated at 50 ° C ⁇ 65 ° C until all solid matter is completely dissolved, the reaction liquid is obtained, the reaction formula is as follows:
  • M includes at least one of a Cd element and a Zn element
  • X includes at least one of an S element or a Se element.
  • each 1 mol of metal oxide or metal hydroxide corresponds to 1 mL to 3 mL of ethanolamine, 0.6 mL to 1.8 mL of mercaptopropionic acid or selenopropionic acid, and 1 mL to 10 mL of solvent dimethoxyethanol, wherein ethanolamine
  • the volume ratio to mercaptopropionic acid or selenopropionic acid was 1:0.6.
  • the step 31 is prepared by adding 1.2 mL of mercaptopropionic acid, 2 mL of ethanolamine, 2 mol of cadmium hydroxide (0.293 g), and 4 mL of dimethoxyethanol to three.
  • the flask was heated under a nitrogen stream purge and heated at 65 ° C until all solid matter was completely dissolved, and a reaction liquid was obtained.
  • Step 32 The reaction solution obtained in the step 31 is centrifuged, and the obtained precipitate is a metal complex M-(XCH 2 COO - H 3 N + CH 2 CH 2 OH) 2 , and the metal complex M-(XCH) 2 COO - H 3 N + CH 2 CH 2 OH) 2 is redispersed in a non-polar solvent to obtain a metal complex solution.
  • the non-polar solvent includes one or more of toluene, chloroform, and n-hexane.
  • Step 4 as shown in FIG. 7, a metal complex solution is dropped on the hole transport layer 50 in each of the through holes 31, and dried to obtain a quantum dot film, and the quantum dot film constitutes a light emitting layer (EL). 60.
  • EL light emitting layer
  • the quantum dot film comprises a red quantum dot film, a blue quantum dot film, and a green quantum dot film.
  • the light-emitting range of the quantum dot film is obtained by adjusting the material type and ratio of the metal complex solution.
  • the red quantum dot film has a light emission range of 630 nm to 690 nm
  • the green quantum dot film has a light emission range of 500 nm to 560 nm
  • the blue quantum dot film has a light emission range of 420 nm to 480 nm.
  • the heating and drying temperature of the metal complex solution is 180 ° C to 250 ° C, preferably 220 ° C to 240 ° C, and more preferably 230 ° C.
  • the red quantum dot film, the blue quantum dot film, and the green quantum dot film have the same drying temperature, which makes the technology have certain advantages compared with the existing OLED device fabrication technology.
  • the R, G, and B organic light-emitting inks generally used in inkjet printing technology differ in parameters such as solvent coefficient and solvent volatilization temperature, resulting in the need to repeatedly adjust the temperature and other parameters, and the technical solution proposed by the present invention, By adjusting the material type and ratio of the metal complex solution, it is possible to form a film of the R, G, B quantum dot film under the same temperature parameter, which simplifies the process.
  • Step 5 an electron transport layer (ETL) 70 is prepared on the light-emitting layer 60 in each of the via holes 31, above the plurality of electron transport layers 70 and the pixel defining layer 30 of the plurality of via holes 31.
  • a cathode 80 is formed.
  • the electron transport layer 70 is prepared by inkjet printing; the cathode 80 is prepared by evaporation.
  • the material of the electron transport layer 70 is an organic material or an inorganic material;
  • the inorganic material includes one or more of ZnO, TiO 2 , WO 3 , and SnO 2 ;
  • the organic material includes 1, 3 , 5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI), and 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2, One or more of 4-triazole (TAZ).
  • the material of the cathode 80 includes one or more of aluminum (Al), silver (Ag), and magnesium silver alloy (MgAg).
  • the present invention further provides a quantum dot light emitting diode display, comprising a substrate 10 , a plurality of anodes 20 disposed on the substrate 10 , and a plurality of anodes 20 , and a pixel defining layer 30 on the plurality of anodes 20 and the substrate 10, wherein the pixel defining layer 30 is provided with a plurality of through holes 31 respectively corresponding to the plurality of anodes 20, each of the through holes 31 being bottom-up
  • the hole injection layer 40, the hole transport layer 50, the light emitting layer 60, and the electron transport layer 70 are sequentially disposed; and further includes a plurality of electron transport layers 70 and the pixel defining layer 30 located in the plurality of through holes 31.
  • Cathode 80 ;
  • the luminescent layer 60 is a quantum dot film formed by forming a metal complex solution, and the metal complex solution is a metal complex M-(XCH 2 COO - H 3 N + CH 2 CH 2 OH) 2 dispersed in A solution obtained in a non-polar solvent, wherein M includes at least one of a Cd element and a Zn element, and X includes at least one of an S element or a Se element.
  • the quantum dot film comprises a red quantum dot film, a blue quantum dot film, and a green quantum dot film.
  • the light-emitting range of the quantum dot film is obtained by adjusting the material type and ratio of the metal complex solution.
  • the red quantum dot film has a light emission range of 630 nm to 690 nm
  • the green quantum dot film has a light emission range of 500 nm to 560 nm
  • the blue quantum dot film has a light emission range of 420 nm to 480 nm.
  • the non-polar solvent includes one or more of toluene, chloroform, and n-hexane.
  • the substrate 10 is a transparent substrate, preferably a glass substrate.
  • the material of the anode 20 is a transparent conductive metal oxide, preferably indium tin oxide.
  • the material of the pixel defining layer 30 is an organic photoresist material, preferably a black organic photoresist material.
  • the material of the hole injection layer 40 includes a polyparaphenylene vinyl compound, a polythiophene compound, a polysilane compound, a triphenylmethane compound, a triarylamine compound, an anthraquinone compound, and a pyrazoline compound.
  • a compound, a azole compound, a carbazole compound, and a butadiene compound is included in the material of the hole injection layer 40.
  • the material of the hole transport layer 50 is an organic material or an inorganic material;
  • the organic material includes 4,4'-N, N'-dicarbazole-biphenyl, N'-diphenyl-N, N'-bis(1-naphthyl)-1,1'-biphenyl-4,4"-diamine, 4,4',4"-tris(N-oxazolyl)-triphenylamine, and N, One or more of N'-bis[4-(N,N'-diphenyl-amino)phenyl]-N,N'-diphenylbenzidine; the inorganic material including NiO, and MoO 3 One or more of them.
  • the material of the electron transport layer 70 is an organic material or an inorganic material;
  • the inorganic material includes one or more of ZnO, TiO 2 , WO 3 , and SnO 2 ;
  • the organic material includes 1, 3 , 5-tris(N-phenylbenzimidazol-2-yl)benzene, and 3-(4-biphenyl)-4-phenyl-5-tert-butylphenyl-1,2,4-tri One or more of the azoles.
  • the material of the cathode 80 includes one or more of aluminum, silver, and magnesium silver alloy.
  • the hole injection layer 40, the hole transport layer 50, the light-emitting layer 60, and the electron transport layer 70 are prepared by an inkjet printing method, and the cathode 80 is prepared by an evaporation method.
  • the quantum dot light emitting diode display of the present invention is formed by using a quantum dot film prepared by a metal complex solution through a film forming method to form a light emitting layer, and an existing ink jet printing method using quantum dot ink.
  • the process parameters are easy to adjust, the process cost is simple, the material cost is reduced, and the sub-pixel level precision control of the inkjet printing technology is adopted to realize the regulation of the three primary colors of R, G and B, without the color film structure, and the thinner industrial design is realized. idea.
  • the quantum dot light-emitting diode display of the invention adopts a quantum dot film to form a light-emitting layer, so that the quantum dot light-emitting diode display has excellent display quality, has simple process and low production cost.

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Abstract

本发明提供一种量子点发光二极管显示器的制作方法及量子点发光二极管显示器。本发明的量子点发光二极管显示器的制作方法，采用由金属配合物溶液通过成膜方法制备出的量子点薄膜构成发光层，与现有的采用量子点墨水的喷墨打印方法相比，工艺参数易调整，工艺制程简单，降低材料成本，通过搭配喷墨印刷技术子像素级别的精确控制，实现R、G、B三原色的调控，无需彩膜结构，实现更轻薄的工业设计理念。本发明的量子点发光二极管显示器，采用量子点薄膜构成发光层，使量子点发光二极管显示器具有优异的显示品质，且制程简单，生产成本低。

Description

量子点发光二极管显示器的制作方法及量子点发光二极管显示器 技术领域
本发明涉及显示技术领域，尤其涉及一种量子点发光二极管显示器的制作方法及量子点发光二极管显示器。
背景技术
OLED(Organic Light-Emitting Diode，有机发光二极管)显示器，也称为有机电致发光显示器，是一种新兴的平板显示装置，由于其具有制备工艺简单、成本低、功耗低、发光亮度高、工作温度适应范围广、体积轻薄、响应速度快，而且易于实现彩色显示和大屏幕显示、易于实现和集成电路驱动器相匹配、易于实现柔性显示等优点，因而具有广阔的应用前景。
半导体材料从体相逐渐减小至一定临界尺寸(1nm～20nm)后，其载流子的波动性变得显著，运动将受限，导致动能的增加，相应的电子结构从体相连续的能级结构变成准分裂的不连续，这一现象称作量子尺寸效应。比较常见的半导体纳米粒子即量子点(Quantum Dot，QD)主要有II-VI，III-V以及IV-VI族元素。这些种类的量子点都十分遵守量子尺寸效应，其性质随尺寸呈现规律性变化，例如吸收及发射波长随尺寸变化而变化。因此，半导体量子点在照明、显示等领域都有着十分重要的应用。
量子点发光材料具有发光光谱集中，色纯度高等优点，近年来以量子点材料为主体的发光显示器件多有报道，目前以量子点材料为发光层的量子点发光二极管(Quantum Dot Light-Emitting Diode，QLED)器件效率已达到20％，相信随着器件结构设计与器件制备技术的进一步发展，该技术指标还会有大幅提升，QLED技术也被誉为较之OLED显示技术更新一代的显示技术。目前，现有技术在制备QLED器件过程中，多采用已经制备好的高质量的量子点材料，混合于溶剂中以溶液成膜的方式制备量子点薄膜，由于量子点材料的尺寸以及表面性质的特殊性，直接导致成膜的方式普遍不理想，直接影响了器件效率。
发明内容
本发明的目的在于提供一种量子点发光二极管显示器的制作方法，工艺参数易调整，工艺制程简单，同时材料成本也大幅度降低。
本发明的目的还在于提供一种量子点发光二极管显示器，具有优异的 显示品质，且制程简单，生产成本低。
为实现上述目的，本发明提供一种量子点发光二极管显示器的制作方法，包括如下步骤：
步骤1、提供一基板，在所述基板上形成数个间隔设置的阳极；在所述数个阳极及基板上形成像素定义层，所述像素定义层上设有分别对应于数个阳极的数个通孔；
步骤2、在所述每个通孔中依次形成设置于阳极上方的空穴注入层、及设于所述空穴注入层上方的空穴传输层；
步骤3、提供金属配合物溶液，所述金属配合物溶液为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2分散于非极性溶剂中得到的溶液，其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种；
步骤4、在每个通孔中的空穴传输层上滴注金属配合物溶液，加热烘干后得到量子点薄膜，所述量子点薄膜构成发光层；
步骤5、在每个通孔中的发光层上制备电子传输层，在数个通孔中的数个电子传输层及像素定义层上方形成阴极。
所述步骤3中，所述金属配合物溶液的制备方法包括如下步骤：
步骤31、将巯基丙酸或硒基丙酸、乙醇胺、以及金属氧化物或金属氢氧化物溶解于二甲氧基乙醇中，在50℃～65℃条件下加热至所有固体物质完全溶解后，得到反应液，反应式如下：
Figure PCTCN2016083061-appb-000001
其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种；
步骤32、对所述步骤31得到的反应液进行离心，得到的沉淀即为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2，将金属配合物M-(XCH2COO-H3N+CH2CH2OH)2重新分散在非极性溶剂中，得到金属配合物溶液。
所述步骤31中，每1moL金属氧化物或金属氢氧化物，对应1mL～3mL乙醇胺、0.6mL～1.8mL巯基丙酸或硒基丙酸、1mL～10mL溶剂二甲氧基乙醇，其中，乙醇胺与巯基丙酸或硒基丙酸的体积比为1：0.6；
所述步骤32中，所述非极性溶剂包括甲苯、氯仿、及正己烷中的一种或多种。
所述步骤1中，所述数个阳极的制备方法为：在所述基板上沉积导电层，采用一道光刻制程对所述导电层进行图形化处理，形成数个阳极；
所述像素定义层的制备方法为：在所述基板、及数个阳极上涂布有机光阻材料，形成光阻层，采用一道光罩对所述光阻层进行曝光显影，分别对应于数个阳极上方形成数个通孔，得到像素定义层。
所述步骤2中，所述空穴注入层、空穴传输层均通过喷墨打印方式制备；
所述步骤5中，所述电子传输层采用喷墨打印方式制备，所述阴极采用蒸镀方式制备。
所述量子点薄膜包括红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜；所述红色量子点薄膜的发光范围为630nm-690nm，所述绿色量子点薄膜的发光范围为500nm-560nm，所述蓝色量子点薄膜的发光范围为420nm-480nm；
所述步骤4中，所述红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜的烘干温度相同。
所述阳极的材料为透明导电金属氧化物；
所述像素定义层的材料为有机光阻材料；
所述空穴注入层的材料包括聚对苯撑乙烯类化合物、聚噻吩类化合物、聚硅烷类化合物、三苯甲烷类化合物、三芳胺类化合物、腙类化合物、吡唑啉类化合物、嚼唑类化合物、咔唑类化合物、及丁二烯类化合物中的一种或多种；
所述空穴传输层的材料为有机材料或无机材料；所述有机材料包括4,4’-N,N’-二咔唑-联苯、N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺、4,4’,4”-三(N-唑基)-三苯胺、及N,N’-二[4-(N,N’-二苯基-氨基)苯基]-N,N’-二苯联苯胺中的一种或多种；所述无机材料包括NiO、及MoO3中的一种或两种；
所述电子传输层的材料为有机材料或无机材料；所述无机材料包括ZnO、TiO2、WO3、及SnO2中的一种或多种；所述有机材料包括1,3,5-三(N-苯基苯并咪唑-2-基)苯、及3-(4-联苯基)-4-苯基-5-叔丁基苯基-1,2,4-三唑中的一种或多种；
所述阴极的材料包括铝、银、及镁银合金中的一种或多种。
本发明还提供一种量子点发光二极管显示器，包括基板、设于所述基板上且间隔设置的数个阳极、及设于所述数个阳极及基板上的像素定义层，所述像素定义层上设有分别对应于数个阳极的数个通孔，每个通孔内 自下而上依次设有空穴注入层、空穴传输层、发光层、及电子传输层；还包括位于所述数个通孔中的数个电子传输层及像素定义层上方的阴极；
所述发光层为由金属配合物溶液成膜制得的量子点薄膜，所述金属配合物溶液为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2分散于非极性溶剂中得到的溶液，其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种。
所述量子点薄膜包括红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜；所述红色量子点薄膜的发光范围为630nm-690nm，所述绿色量子点薄膜的发光范围为500nm-560nm，所述蓝色量子点薄膜的发光范围为420nm-480nm。
所述非极性溶剂包括甲苯、氯仿、及正己烷中的一种或多种。
所述阳极的材料为透明导电金属氧化物；
所述像素定义层的材料为有机光阻材料；
所述空穴注入层的材料包括聚对苯撑乙烯类化合物、聚噻吩类化合物、聚硅烷类化合物、三苯甲烷类化合物、三芳胺类化合物、腙类化合物、吡唑啉类化合物、嚼唑类化合物、咔唑类化合物、及丁二烯类化合物中的一种或多种；
所述空穴传输层的材料为有机材料或无机材料；所述有机材料包括4,4’-N,N’-二咔唑-联苯、N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺、4,4’,4”-三(N-唑基)-三苯胺、及N,N’-二[4-(N,N’-二苯基-氨基)苯基]-N,N’-二苯联苯胺中的一种或多种；所述无机材料包括NiO及MoO3中的一种或多种；
所述电子传输层的材料为有机材料或无机材料；所述无机材料包括ZnO、TiO2、WO3、及SnO2中的一种或多种；所述有机材料包括1,3,5-三(N-苯基苯并咪唑-2-基)苯、及3-(4-联苯基)-4-苯基-5-叔丁基苯基-1,2,4-三唑中的一种或两种；
所述阴极的材料包括铝、银、及镁银合金中的一种或多种。
本发明还提供一种量子点发光二极管显示器的制作方法，包括如下步骤：
步骤1、提供一基板，在所述基板上形成数个间隔设置的阳极；在所述数个阳极及基板上形成像素定义层，所述像素定义层上设有分别对应于数个阳极的数个通孔；
步骤2、在所述每个通孔中依次形成设置于阳极上方的空穴注入层、及设于所述空穴注入层上方的空穴传输层；
步骤3、提供金属配合物溶液，所述金属配合物溶液为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2分散于非极性溶剂中得到的溶液，其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种；
步骤4、在每个通孔中的空穴传输层上滴注金属配合物溶液，加热烘干后得到量子点薄膜，所述量子点薄膜构成发光层；
步骤5、在每个通孔中的发光层上制备电子传输层，在数个通孔中的数个电子传输层及像素定义层上方形成阴极；
其中，所述步骤3中，所述金属配合物溶液的制备方法包括如下步骤：
步骤31、将巯基丙酸或硒基丙酸、乙醇胺、以及金属氧化物或金属氢氧化物溶解于二甲氧基乙醇中，在50℃～65℃条件下加热至所有固体物质完全溶解后，得到反应液，反应式如下：
Figure PCTCN2016083061-appb-000002
其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种；
步骤32、对所述步骤31得到的反应液进行离心，得到的沉淀即为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2，将金属配合物M-(XCH2COO-H3N+CH2CH2OH)2重新分散在非极性溶剂中，得到金属配合物溶液；
其中，所述步骤1中，所述数个阳极的制备方法为：在所述基板上沉积导电层，采用一道光刻制程对所述导电层进行图形化处理，形成数个阳极；
所述像素定义层的制备方法为：在所述基板、及数个阳极上涂布有机光阻材料，形成光阻层，采用一道光罩对所述光阻层进行曝光显影，分别对应于数个阳极上方形成数个通孔，得到像素定义层；
所述步骤2中，所述空穴注入层、空穴传输层均通过喷墨打印方式制备；
所述步骤5中，所述电子传输层采用喷墨打印方式制备，所述阴极采用蒸镀方式制备。
本发明的有益效果：本发明提供的量子点发光二极管显示器的制作方法，采用由金属配合物溶液通过成膜方法制备出的量子点薄膜构成发光层，与现有的采用量子点墨水的喷墨打印方法相比，工艺参数易调整，工 艺制程简单，降低材料成本，通过搭配喷墨印刷技术子像素级别的精确控制，实现R、G、B三原色的调控，无需彩膜结构，实现更轻薄的工业设计理念。本发明提供的量子点发光二极管显示器，采用量子点薄膜构成发光层，使量子点发光二极管显示器具有优异的显示品质，且制程简单，生产成本低。
为了能更进一步了解本发明的特征以及技术内容，请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明用，并非用来对本发明加以限制。
附图说明
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案及其它有益效果显而易见。
附图中，
图1为本发明的量子点发光二极管显示器的制作方法的流程图；
图2-5为本发明的量子点发光二极管显示器的制作方法的步骤1的示意图；
图6为本发明的量子点发光二极管显示器的制作方法的步骤2的示意图；
图7为本发明的量子点发光二极管显示器的制作方法的步骤4的示意图；
图8为本发明的量子点发光二极管显示器的制作方法的步骤5的示意图暨本发明的量子点发光二极管显示器的结构示意图。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果，以下结合本发明的优选实施例及其附图进行详细描述。
请参阅图1，本发明首先提供一种量子点发光二极管显示器的制作方法，包括如下步骤：
步骤1、如图2-5所示，提供一基板10，在所述基板10上形成数个间隔设置的阳极20；在所述数个阳极20及基板10上形成像素定义层(Bank)30，所述像素定义层30上设有分别对应于数个阳极20的数个通孔31。
具体的，所述数个阳极20的制备方法为：如图2-3所示，在所述基板10上沉积导电层15，采用一道光刻制程对所述导电层15进行图形化处理形成数个阳极20。
具体的，所述基板10为透明基板，优选为玻璃基板。
具体的，所述阳极20的材料为透明导电金属氧化物，优选为氧化铟锡(ITO)。
具体的，所述像素定义层30的制备方法为：如图4-5所示，在所述基板10、及数个阳极20上涂布有机光阻材料，形成光阻层25，采用一道光罩对所述光阻层25进行图形化处理，分别对应于数个阳极20上方形成数个通孔31，得到像素定义层30。
优选的，所述像素定义层30的材料为黑色有机光阻材料。
步骤2、如图6所示，在所述每个通孔31中依次形成设置于阳极20上方的空穴注入层(HIL)40、及设于所述空穴注入层40上方的空穴传输层(HTL)50。
具体的，所述空穴注入层40的材料包括聚对苯撑乙烯(PPV)类化合物、聚噻吩类化合物、聚硅烷类化合物、三苯甲烷类化合物、三芳胺类化合物、腙类化合物、吡唑啉类化合物、嚼唑类化合物、咔唑类化合物、及丁二烯类化合物中的一种或多种。
具体的，所述空穴传输层50的材料为有机材料或无机材料；所述有机材料包括4,4’-N,N’-二咔唑-联苯(CBP)、N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺(a-NPD)、4,4’,4”-三(N-唑基)-三苯胺(TCCA)、及N,N’-二[4-(N,N’-二苯基-氨基)苯基]-N,N’-二苯联苯胺(DNTPD)中的一种或多种；所述无机材料包括NiO、及MoO3中的一种或多种。
具体的，所述空穴注入层40、空穴传输层50均通过喷墨打印(Ink Jet Printer，IJP)方式制备。
步骤3、提供金属配合物溶液，所述金属配合物溶液为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2分散于非极性溶剂中得到的溶液，其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种。
具体的，所述金属配合物溶液的制备方法包括如下步骤：
步骤31、将巯基丙酸(HSCH2COOH)或硒基丙酸(HSeCH2COOH)、乙醇胺(H2NCH2CH2OH)、以及金属氧化物(MO)或金属氢氧化物(M(OH)2)溶解于二甲氧基乙醇中，在50℃～65℃条件下加热至所有固体物质完全溶解后，得到反应液，反应式如下：
Figure PCTCN2016083061-appb-000003
上述反应式中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种。
所述步骤31中，每1moL金属氧化物或金属氢氧化物，对应1mL～3mL乙醇胺、0.6mL～1.8mL巯基丙酸或硒基丙酸、1mL～10mL溶剂二甲氧基乙醇，其中，乙醇胺与巯基丙酸或硒基丙酸的体积比为1：0.6。
例如，当目的是制备CdS量子点薄膜时，所述步骤31的制备方法为：取1.2mL巯基丙酸、2mL乙醇胺、2mol氢氧化镉(0.293g)、以及4mL二甲氧基乙醇添加于三颈烧瓶中，在氮气流吹送保护下，在65℃条件下加热至所有固体物质完全溶解后，得到反应液。
步骤32、对所述步骤31得到的反应液进行离心，得到的沉淀即为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2 ，将金属配合物M-(XCH2COO-H3N+CH2CH2OH)2重新分散在非极性溶剂中，得到金属配合物溶液。
具体的，所述非极性溶剂包括甲苯、氯仿、及正己烷中的一种或多种。
步骤4、如图7所示，在每个通孔31中的空穴传输层50上滴注金属配合物溶液，加热烘干后得到量子点薄膜，所述量子点薄膜构成发光层(EL)60。
具体的，所述量子点薄膜包括红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜。所述量子点薄膜的发光范围通过调整调整金属配合物溶液的材料种类与配比得到。所述红色量子点薄膜的发光范围为630nm-690nm，所述绿色量子点薄膜的发光范围为500nm-560nm，所述蓝色量子点薄膜的发光范围为420nm-480nm。
具体的，所述步骤4中，对金属配合物溶液的加热烘干温度为180℃～250℃，优选为220℃～240℃，更优选为230℃。
具体的，所述步骤4中，所述红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜的烘干温度相同，这使得该技术与现有OLED器件制备技术相比具有一定的优势，通常搭配喷墨打印技术使用的R、G、B有机发光墨水由于溶剂系数的差别，溶剂挥发温度等参数也有所区别，造成需要反复调整温度等参数的现状，而本发明提出的技术方案，通过调整金属配合物溶液的材料种类与配比，能够实现R、G、B量子点薄膜在相同的温度参数下成膜，简化了这一工艺过程。
步骤5、如图8所示，在每个通孔31中的发光层60上制备电子传输层(ETL)70，在数个通孔31中的数个电子传输层70及像素定义层30上方形成阴极(Cathode)80。
至此，完成量子点发光二极管显示器的制备过程。
具体的，所述电子传输层70采用喷墨打印方式制备；所述阴极80采用蒸镀方式制备。
具体的，所述电子传输层70的材料为有机材料或无机材料；所述无机材料包括ZnO、TiO2、WO3、及SnO2中的一种或多种；所述有机材料包括1,3,5-三(N-苯基苯并咪唑-2-基)苯(TPBI)、及3-(4-联苯基)-4-苯基-5-叔丁基苯基-1,2,4-三唑(TAZ)中的一种或多种。
具体的，所述阴极80的材料包括铝(Al)、银(Ag)、及镁银合金(MgAg)中的一种或多种。
请参阅图8，基于上述量子点发光二极管显示器的制作方法，本发明还提供一种量子点发光二极管显示器，包括基板10、设于所述基板10上其间隔设置的数个阳极20、及设于所述数个阳极20及基板10上的像素定义层30，所述像素定义层30上设有分别对应于数个阳极20的数个通孔31，每个通孔31内自下而上依次设有空穴注入层40、空穴传输层50、发光层60、及电子传输层70；还包括位于所述数个通孔31中的数个电子传输层70及像素定义层30上方的阴极80；
所述发光层60为由金属配合物溶液成膜制得的量子点薄膜，所述金属配合物溶液为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2分散于非极性溶剂中得到的溶液，其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种。
具体的，所述量子点薄膜包括红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜。所述量子点薄膜的发光范围通过调整调整金属配合物溶液的材料种类与配比得到。所述红色量子点薄膜的发光范围为630nm-690nm，所述绿色量子点薄膜的发光范围为500nm-560nm，所述蓝色量子点薄膜的发光范围为420nm-480nm。
具体的，所述非极性溶剂包括甲苯、氯仿、及正己烷中的一种或多种。
具体的，所述基板10为透明基板，优选为玻璃基板。
具体的，所述阳极20的材料为透明导电金属氧化物，优选为氧化铟锡。
具体的，所述像素定义层30的材料为有机光阻材料，优选为黑色有机光阻材料。
具体的，所述空穴注入层40的材料包括聚对苯撑乙烯类化合物、聚噻吩类化合物、聚硅烷类化合物、三苯甲烷类化合物、三芳胺类化合物、腙类化合物、吡唑啉类化合物、嚼唑类化合物、咔唑类化合物、及丁二烯类化合物中的一种或多种。
具体的，所述空穴传输层50的材料为有机材料或无机材料；所述有机材料包括4,4’-N,N’-二咔唑-联苯、N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺、4,4’,4”-三(N-唑基)-三苯胺、及N,N’-二[4-(N,N’-二苯基-氨基)苯基]-N,N’-二苯联苯胺中的一种或多种；所述无机材料包括NiO、及MoO3中的一种或多种。
具体的，所述电子传输层70的材料为有机材料或无机材料；所述无机材料包括ZnO、TiO2、WO3、及SnO2中的一种或多种；所述有机材料包括1,3,5-三(N-苯基苯并咪唑-2-基)苯、及3-(4-联苯基)-4-苯基-5-叔丁基苯基-1,2,4-三唑中的一种或多种。
具体的，所述阴极80的材料包括铝、银、及镁银合金中的一种或多种。
具体的，所述空穴注入层40、空穴传输层50、发光层60、电子传输层70由喷墨打印方式制备，所述阴极80通过蒸镀方式制备。
综上所述，本发明的量子点发光二极管显示器的制作方法，采用由金属配合物溶液通过成膜方法制备出的量子点薄膜构成发光层，与现有的采用量子点墨水的喷墨打印方法相比，工艺参数易调整，工艺制程简单，降低材料成本，通过搭配喷墨印刷技术子像素级别的精确控制，实现R、G、B三原色的调控，无需彩膜结构，实现更轻薄的工业设计理念。本发明的量子点发光二极管显示器，采用量子点薄膜构成发光层，使量子点发光二极管显示器具有优异的显示品质，且制程简单，生产成本低。
以上所述，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思作出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。

Claims (14)

  1. 一种量子点发光二极管显示器的制作方法，包括如下步骤：
    步骤1、提供一基板，在所述基板上形成数个间隔设置的阳极；在所述数个阳极及基板上形成像素定义层，所述像素定义层上设有分别对应于数个阳极的数个通孔；
    步骤2、在所述每个通孔中依次形成设置于阳极上方的空穴注入层、及设于所述空穴注入层上方的空穴传输层；
    步骤3、提供金属配合物溶液，所述金属配合物溶液为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2分散于非极性溶剂中得到的溶液，其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种；
    步骤4、在每个通孔中的空穴传输层上滴注金属配合物溶液，加热烘干后得到量子点薄膜，所述量子点薄膜构成发光层；
    步骤5、在每个通孔中的发光层上制备电子传输层，在数个通孔中的数个电子传输层及像素定义层上方形成阴极。
  2. 如权利要求1所述的量子点发光二极管显示器的制作方法，其中，所述步骤3中，所述金属配合物溶液的制备方法包括如下步骤：
    步骤31、将巯基丙酸或硒基丙酸、乙醇胺、以及金属氧化物或金属氢氧化物溶解于二甲氧基乙醇中，在50℃～65℃条件下加热至所有固体物质完全溶解后，得到反应液，反应式如下：
    Figure PCTCN2016083061-appb-100001
    其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种；
    步骤32、对所述步骤31得到的反应液进行离心，得到的沉淀即为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2，将金属配合物M-(XCH2COO-H3N+CH2CH2OH)2重新分散在非极性溶剂中，得到金属配合物溶液。
  3. 如权利要求2所述的量子点发光二极管显示器的制作方法，其中，所述步骤31中，每1moL金属氧化物或金属氢氧化物，对应1mL～3mL乙醇胺、0.6mL～1.8mL巯基丙酸或硒基丙酸、1mL～10mL溶剂二甲氧基乙醇， 其中，乙醇胺与巯基丙酸或硒基丙酸的体积比为1：0.6；
    所述步骤32中，所述非极性溶剂包括甲苯、氯仿、及正己烷中的一种或多种。
  4. 如权利要求1所述的量子点发光二极管显示器的制作方法，其中，所述步骤1中，所述数个阳极的制备方法为：在所述基板上沉积导电层，采用一道光刻制程对所述导电层进行图形化处理，形成数个阳极；
    所述像素定义层的制备方法为：在所述基板、及数个阳极上涂布有机光阻材料，形成光阻层，采用一道光罩对所述光阻层进行曝光显影，分别对应于数个阳极上方形成数个通孔，得到像素定义层；
    所述步骤2中，所述空穴注入层、空穴传输层均通过喷墨打印方式制备；
    所述步骤5中，所述电子传输层采用喷墨打印方式制备，所述阴极采用蒸镀方式制备。
  5. 如权利要求1所述的量子点发光二极管显示器的制作方法，其中，所述量子点薄膜包括红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜；所述红色量子点薄膜的发光范围为630nm-690nm，所述绿色量子点薄膜的发光范围为500nm-560nm，所述蓝色量子点薄膜的发光范围为420nm-480nm；
    所述步骤4中，所述红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜的烘干温度相同。
  6. 如权利要求1所述的量子点发光二极管显示器的制作方法，其中，所述阳极的材料为透明导电金属氧化物；
    所述像素定义层的材料为有机光阻材料；
    所述空穴注入层的材料包括聚对苯撑乙烯类化合物、聚噻吩类化合物、聚硅烷类化合物、三苯甲烷类化合物、三芳胺类化合物、腙类化合物、吡唑啉类化合物、嚼唑类化合物、咔唑类化合物、及丁二烯类化合物中的一种或多种；
    所述空穴传输层的材料为有机材料或无机材料；所述有机材料包括4,4’-N,N’-二咔唑-联苯、N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺、4,4’,4”-三(N-唑基)-三苯胺、及N,N’-二[4-(N,N’-二苯基-氨基)苯基]-N,N’-二苯联苯胺中的一种或多种；所述无机材料包括NiO、及MoO3中的一种或多种；
    所述电子传输层的材料为有机材料或无机材料；所述无机材料包括ZnO、TiO2、WO3、及SnO2中的一种或多种；所述有机材料包括1,3,5-三(N- 苯基苯并咪唑-2-基)苯、及3-(4-联苯基)-4-苯基-5-叔丁基苯基-1,2,4-三唑中的一种或两种；
    所述阴极的材料包括铝、银、及镁银合金中的一种或多种。
  7. 一种量子点发光二极管显示器，包括基板、设于所述基板上且间隔设置的数个阳极、及设于所述数个阳极及基板上的像素定义层，所述像素定义层上设有分别对应于数个阳极的数个通孔，每个通孔内自下而上依次设有空穴注入层、空穴传输层、发光层、及电子传输层；还包括位于所述数个通孔中的数个电子传输层及像素定义层上方的阴极；
    所述发光层为由金属配合物溶液成膜制得的量子点薄膜，所述金属配合物溶液为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2分散于非极性溶剂中得到的溶液，其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种。
  8. 如权利要求7所述的量子点发光二极管显示器，其中，所述量子点薄膜包括红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜；所述红色量子点薄膜的发光范围为630nm-690nm，所述绿色量子点薄膜的发光范围为500nm-560nm，所述蓝色量子点薄膜的发光范围为420nm-480nm。
  9. 如权利要求7所述的量子点发光二极管显示器，其中，所述非极性溶剂包括甲苯、氯仿、及正己烷中的一种或多种。
  10. 如权利要求7所述的量子点发光二极管显示器，其中，
    所述阳极的材料为透明导电金属氧化物；
    所述像素定义层的材料为有机光阻材料；
    所述空穴注入层的材料包括聚对苯撑乙烯类化合物、聚噻吩类化合物、聚硅烷类化合物、三苯甲烷类化合物、三芳胺类化合物、腙类化合物、吡唑啉类化合物、嚼唑类化合物、咔唑类化合物、及丁二烯类化合物中的一种或多种；
    所述空穴传输层的材料为有机材料或无机材料；所述有机材料包括4,4’-N,N’-二咔唑-联苯、N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺、4,4’,4”-三(N-唑基)-三苯胺、及N,N’-二[4-(N,N’-二苯基-氨基)苯基]-N,N’-二苯联苯胺中的一种或多种；所述无机材料包括NiO、及MoO3中的一种或多种；
    所述电子传输层的材料为有机材料或无机材料；所述无机材料包括ZnO、TiO2、WO3、及SnO2中的一种或多种；所述有机材料包括1,3,5-三(N-苯基苯并咪唑-2-基)苯、及3-(4-联苯基)-4-苯基-5-叔丁基苯基-1,2,4-三唑中的一种或多种；
    所述阴极的材料包括铝、银、及镁银合金中的一种或多种。
  11. 一种量子点发光二极管显示器的制作方法，包括如下步骤：
    步骤1、提供一基板，在所述基板上形成数个间隔设置的阳极；在所述数个阳极及基板上形成像素定义层，所述像素定义层上设有分别对应于数个阳极的数个通孔；
    步骤2、在所述每个通孔中依次形成设置于阳极上方的空穴注入层、及设于所述空穴注入层上方的空穴传输层；
    步骤3、提供金属配合物溶液，所述金属配合物溶液为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2分散于非极性溶剂中得到的溶液，其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种；
    步骤4、在每个通孔中的空穴传输层上滴注金属配合物溶液，加热烘干后得到量子点薄膜，所述量子点薄膜构成发光层；
    步骤5、在每个通孔中的发光层上制备电子传输层，在数个通孔中的数个电子传输层及像素定义层上方形成阴极；
    其中，所述步骤3中，所述金属配合物溶液的制备方法包括如下步骤：
    步骤31、将巯基丙酸或硒基丙酸、乙醇胺、以及金属氧化物或金属氢氧化物溶解于二甲氧基乙醇中，在50℃～65℃条件下加热至所有固体物质完全溶解后，得到反应液，反应式如下：
    Figure PCTCN2016083061-appb-100002
    其中，M包括Cd元素和Zn元素中的至少一种，X包括S元素或Se元素中的至少一种；
    步骤32、对所述步骤31得到的反应液进行离心，得到的沉淀即为金属配合物M-(XCH2COO-H3N+CH2CH2OH)2，将金属配合物M-(XCH2COO-H3N+CH2CH2OH)2重新分散在非极性溶剂中，得到金属配合物溶液；
    其中，所述步骤1中，所述数个阳极的制备方法为：在所述基板上沉积导电层，采用一道光刻制程对所述导电层进行图形化处理，形成数个阳极；
    所述像素定义层的制备方法为：在所述基板、及数个阳极上涂布有机光阻材料，形成光阻层，采用一道光罩对所述光阻层进行曝光显影，分别对应于数个阳极上方形成数个通孔，得到像素定义层；
    所述步骤2中，所述空穴注入层、空穴传输层均通过喷墨打印方式制备；
    所述步骤5中，所述电子传输层采用喷墨打印方式制备，所述阴极采用蒸镀方式制备。
  12. 如权利要求11所述的量子点发光二极管显示器的制作方法，其中，所述步骤31中，每1moL金属氧化物或金属氢氧化物，对应1mL～3mL乙醇胺、0.6mL～1.8mL巯基丙酸或硒基丙酸、1mL～10mL溶剂二甲氧基乙醇，其中，乙醇胺与巯基丙酸或硒基丙酸的体积比为1：0.6；
    所述步骤32中，所述非极性溶剂包括甲苯、氯仿、及正己烷中的一种或多种。
  13. 如权利要求11所述的量子点发光二极管显示器的制作方法，其中，所述量子点薄膜包括红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜；所述红色量子点薄膜的发光范围为630nm-690nm，所述绿色量子点薄膜的发光范围为500nm-560nm，所述蓝色量子点薄膜的发光范围为420nm-480nm；
    所述步骤4中，所述红色量子点薄膜、蓝色量子点薄膜、及绿色量子点薄膜的烘干温度相同。
  14. 如权利要求11所述的量子点发光二极管显示器的制作方法，其中，所述阳极的材料为透明导电金属氧化物；
    所述像素定义层的材料为有机光阻材料；
    所述空穴注入层的材料包括聚对苯撑乙烯类化合物、聚噻吩类化合物、聚硅烷类化合物、三苯甲烷类化合物、三芳胺类化合物、腙类化合物、吡唑啉类化合物、嚼唑类化合物、咔唑类化合物、及丁二烯类化合物中的一种或多种；
    所述空穴传输层的材料为有机材料或无机材料；所述有机材料包括4,4’-N,N’-二咔唑-联苯、N’-二苯基-N,N’-二(1-萘基)-1,1’-联苯基-4,4”-二胺、4,4’,4”-三(N-唑基)-三苯胺、及N,N’-二[4-(N,N’-二苯基-氨基)苯基]-N,N’-二苯联苯胺中的一种或多种；所述无机材料包括NiO、及MoO3中的一种或多种；
    所述电子传输层的材料为有机材料或无机材料；所述无机材料包括ZnO、TiO2、WO3、及SnO2中的一种或多种；所述有机材料包括1,3,5-三(N-苯基苯并咪唑-2-基)苯、及3-(4-联苯基)-4-苯基-5-叔丁基苯基-1,2,4-三唑中的一种或两种；
    所述阴极的材料包括铝、银、及镁银合金中的一种或多种。
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