WO2022036652A1 - 发光二极管器件、显示面板、显示装置和制作方法 - Google Patents

发光二极管器件、显示面板、显示装置和制作方法 Download PDF

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WO2022036652A1
WO2022036652A1 PCT/CN2020/110338 CN2020110338W WO2022036652A1 WO 2022036652 A1 WO2022036652 A1 WO 2022036652A1 CN 2020110338 W CN2020110338 W CN 2020110338W WO 2022036652 A1 WO2022036652 A1 WO 2022036652A1
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quantum dot
substrate
layer
light
emitting diode
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PCT/CN2020/110338
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English (en)
French (fr)
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梅文海
张宜驰
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京东方科技集团股份有限公司
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Priority to US17/296,839 priority Critical patent/US11877461B2/en
Priority to PCT/CN2020/110338 priority patent/WO2022036652A1/zh
Priority to CN202080001652.0A priority patent/CN114641869A/zh
Publication of WO2022036652A1 publication Critical patent/WO2022036652A1/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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • 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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/80—Manufacture or treatment specially adapted for the organic devices covered by this subclass using temporary substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • 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 technical field of semiconductors, and in particular, to a light emitting diode device, a display panel, a display device and a manufacturing method.
  • QLED Quantum Dots Light Emitting Doide Display
  • QLED has the advantages of narrow emission peak, high color saturation, and wide color gamut.
  • Embodiments of the present disclosure provide a light emitting diode device, including:
  • a first electrode located on one side of the base substrate
  • a carrier functional layer located on the side of the first electrode away from the base substrate;
  • the quantum dot light-emitting layer is located on the side of the carrier functional layer away from the first electrode, and the quantum dot light-emitting layer has a molecular chain structure inside, wherein the molecular chain structure is modified by the first reactant and
  • the molecule undergoes atom transfer radical polymerization to form, and the first reactant includes a quantum dot body and a ligand molecule A connected to the quantum dot body, and the first reactant is connected to the quantum dot body through the ligand molecule A.
  • the modified molecule undergoes an atom transfer radical polymerization reaction, and the initial state of the modified molecule is to connect to the side of the functional layer of the carrier facing the light-emitting layer of the quantum dot;
  • the second electrode is located on the side of the quantum dot light-emitting layer away from the carrier functional layer.
  • the general formula of the ligand molecule A is:
  • R1 is an electron donating group
  • R2 is a solubilizing group
  • R1 includes one of the following:
  • R2 includes one of the following:
  • the general formula of the modified molecule is:
  • R3 is a group coupled with the surface of the carrier functional layer
  • R6 is a halogenated group
  • R5 is an electron donating group
  • R3 includes one of the following:
  • R6 includes one of the following:
  • R5 includes one of the following:
  • R4 includes one of the following:
  • the first reactant includes a ligand molecule B, and the general formula of the ligand molecule B is:
  • 1 ⁇ n3 ⁇ 12, 1 ⁇ m3 ⁇ 12, R9 is a group that coordinates with the quantum dot body
  • R11 is a group that forms a hydrogen bond with the intermediate substrate when transferring the quantum dot light-emitting layer.
  • R9 includes one of the following:
  • R11 includes one of the following:
  • R7 includes one of the following:
  • R8 includes one of the following:
  • R10 includes one of the following:
  • the structure of the quantum dot body connected with the ligand molecule A is:
  • the modified molecule is:
  • the chain-initiated reaction that occurs on the surface of the quantum dot light-emitting layer facing the carrier functional layer is:
  • the structure of the molecular chain structure is:
  • the chain growth reaction that occurs inside the quantum dot light-emitting layer is:
  • the material of the carrier functional layer is an inorganic metal oxide, and the surface of the inorganic metal oxide has hydroxyl groups.
  • the first electrode is a cathode
  • the second electrode is an anode
  • the carrier functional layer is an electron transport layer
  • the material of the electron transport layer is zinc oxide
  • the first electrode is an anode
  • the second electrode is a cathode
  • the carrier functional layer is a hole transport layer
  • the material of the hole transport layer is nickel oxide.
  • Embodiments of the present disclosure further provide a display panel, including the light emitting diode device provided by the embodiments of the present disclosure.
  • Embodiments of the present disclosure further provide a display device, which includes the display panel provided by the embodiments of the present disclosure.
  • Embodiments of the present disclosure also provide a method for fabricating a light-emitting diode device, including:
  • a quantum dot film layer including a first reactant is formed on the carrier substrate, the first reactant includes a quantum dot body, a ligand molecule A connected to the quantum dot body, and a ligand connected to the quantum dot body body molecule B;
  • the intermediate substrate with the quantum dot film layer is attached to the base substrate formed with the modified molecules, so that the ligand molecule A of the first reactant on the surface of the quantum dot film layer is combined with
  • the modified molecule undergoes an atom transfer radical polymerization reaction, and a continuous atom transfer radical polymerization reaction is performed inside the quantum dot film layer to form a quantum dot light-emitting layer, wherein the base substrate is formed with a first electrode and a the carrier functional layer on the side of the first electrode facing away from the base substrate, and the modified molecule is connected to the surface of the carrier functional layer facing away from the first electrode;
  • a second electrode is formed.
  • the forming the quantum dot film layer including the first reactant on the carrier substrate includes:
  • a solution containing ligand molecule A and ligand molecule B is formed on the carrier substrate on which the initial quantum dot film layer is formed, so that the ligand molecule A, the ligand molecule B and the initial ligand are formed A ligand exchange reaction occurs.
  • the forming an initial quantum dot film layer with initial ligands on the carrier substrate includes:
  • the silicon-based substrate is treated with octadecanetrimethoxysilicon
  • An initial quantum dot film layer with oleic acid ligands is formed on the silicon-based substrate.
  • the manufacturing method before laminating the intermediate substrate with the quantum dot film layer and the base substrate formed with the carrier functional layer of the modified molecule, the manufacturing method further includes:
  • a solution containing the modified molecule is formed on the surface of the carrier functional layer, so that the modified molecule is coupled with the hydroxyl groups on the surface of the carrier functional layer.
  • the The production method also includes:
  • the intermediate substrate with the quantum dot film layer adhered is contacted with a gravure plate with grooves to form a patterned quantum dot film layer.
  • the manufacturing method when laminating the intermediate substrate with the quantum dot film layer and the base substrate formed with modified molecules, the manufacturing method further includes:
  • the step of contacting the quantum dot film layer through the intermediate substrate includes:
  • the quantum dot film layer is contacted through a substrate made of polydimethylsiloxane.
  • FIG. 1 is a schematic structural diagram of a light emitting diode device according to an embodiment of the present disclosure
  • FIG. 2 is a schematic diagram of binding of a ligand of a quantum dot film layer to a modified molecule C of a substrate according to an embodiment of the present disclosure
  • FIG. 3 is a schematic diagram of a manufacturing process of a light emitting diode device according to an embodiment of the present disclosure
  • FIG. 4 is a schematic diagram of a manufacturing process of a light emitting diode device according to an embodiment of the present disclosure
  • FIG. 5 is a schematic diagram of a manufacturing process of a specific light emitting diode device according to an embodiment of the present disclosure
  • FIG. 6 is a schematic diagram of a manufacturing process of a light emitting diode device forming a patterned quantum dot film layer according to an embodiment of the present disclosure
  • FIG. 7 is a schematic diagram of a specific transfer process of a quantum dot film layer according to an embodiment of the present disclosure.
  • an embodiment of the present disclosure provides a light emitting diode device, including:
  • the first electrode 2 is located on one side of the base substrate 1. Specifically, the first electrode 2 may be a plurality of structures spaced apart from each other;
  • the carrier functional layer 3 is located on the side of the first electrode 2 away from the base substrate 1.
  • the carrier functional layer 3 may be a plurality of structures spaced from each other and corresponding to the first electrodes 2 one-to-one.
  • the orthographic projection of an electrode 2 on the substrate substrate 1 can cover the orthographic projection of the corresponding carrier functional layer 3 on the substrate substrate; specifically, the light-emitting diode device can also have a blocking wall 7, which is used to separate the color of the light.
  • Different sub-light-emitting devices 80 (as shown in FIG.
  • each sub-light-emitting device 80 includes a first electrode 2.
  • FIG. 1 is only an example of the light-emitting diode device having two sub-light-emitting devices 80.
  • the light-emitting diode device can be There are more sub-light-emitting devices 80, and the embodiment of the present disclosure is not limited thereto).
  • the quantum dot light-emitting layer 4 is located on the side of the carrier functional layer 3 away from the first electrode 2.
  • the quantum dot light-emitting layer 4 has a molecular chain structure X inside, wherein the molecular chain structure X is composed of the first reactant and the modification molecule C.
  • Atom Transfer Radical Polymerization occurs, as shown in Figure 2, where PDMS (polydimethylsiloxane (PDMS)) is used for transferring the quantum dot light-emitting layer.
  • the first reactant includes the quantum dot body QD and the ligand molecule A connected to the quantum dot body QD
  • the first reactant undergoes an atom transfer radical polymerization reaction with the modified molecule C through the ligand molecule A, and the modified molecule C is initially connected to the side of the carrier functional layer 3 facing the quantum dot light-emitting layer 4, that is, before the During the atom transfer radical polymerization reaction, the modified molecule C can be first formed on the surface of the carrier functional layer 3 facing the quantum dot light-emitting layer 4, and the quantum dot light-emitting layer 3 is a film layer with the first reactant.
  • the carrier functional layer 3 when the carrier functional layer 3 is in contact with the quantum dot light-emitting layer 4, since the ligand molecule A in the first reactant can undergo an atom transfer radical polymerization reaction with the modified molecule C, and then can First, the first reactant on the surface of the quantum dot light-emitting layer 3 is combined with the modified molecule C. With the further occurrence of the atom transfer radical polymerization reaction, the first reactant inside the quantum dot light-emitting layer 3 also reacts to form molecular chains. structure, so that the entire quantum dot light-emitting layer 3 forms an overall structure that is combined with each other by the molecular chain structure X; the quantum dot body can be a conventional quantum dot light-emitting material;
  • the second electrode 5 is located on the side of the quantum dot light-emitting layer 4 away from the carrier functional layer 3 .
  • the second electrode 5 may have a whole-layer structure.
  • the second electrodes 5 may also be spaced apart from each other.
  • the quantum dot light emitting layer 4 has a molecular chain structure X formed by the atom transfer radical polymerization reaction of the first reactant and the modified molecule C, that is, the quantum dot light emitting layer 4 faces the carrier.
  • the first surface 41 of the carrier functional layer 3, the second surface 42 of the quantum dot light-emitting layer 4 facing the second electrode 5, and the region between the first surface 41 and the second surface 42 all have a molecular chain structure X, and the entire
  • the quantum dot light-emitting layer 4 as a whole forms an overall structure in which the molecular chain structure X is combined with each other, and the quantum dot light-emitting layer 4 is transferred from the original carrier substrate to the substrate of the light-emitting diode device by transferring the transfer substrate.
  • the quantum dot light-emitting layer 4 can be transferred as a whole structure from the intermediate substrate to the base substrate 1.
  • the quantum dot light-emitting layer 4 When the quantum dot light-emitting layer 4 only has the quantum dot body in the prior art, it can only transfer the quantum dot light-emitting layer 4 to the base substrate 1. Part of the quantum dot light-emitting layer on the surface of the intermediate substrate is transferred to the base substrate, resulting in a problem that the transfer yield of the light-emitting diode device is low.
  • the structural feature of the ligand molecule A is that it contains styrene and its derivatives, acrylate and its derivatives, acrylamide and its derivatives, acrylonitrile and the like.
  • the general formula of the ligand molecule A is: Among them, R1 is an electron-donating group, and R2 is a solubilizing group.
  • the ligand molecule A is R1 can provide electrons for the ATRP reaction, which is beneficial to the ATRP reaction, and R2 can increase the solubility, which is beneficial to the preparation of the ligand molecule A on the QD of the quantum dot body.
  • the structures other than R2 in the ligand molecule A may contain styrene and its derivatives, acrylate and its derivatives, acrylamide and its derivatives, acrylonitrile and the like.
  • R1 may include one of the following: -S-.
  • R2 includes one of the following: -(CH 2 ) n1 -; Among them, 1 ⁇ n1 ⁇ 8, 1 ⁇ m1 ⁇ 8.
  • the general formula of modified molecule C is: Wherein, R3 is a group coupled with the surface of the carrier functional layer, R6 is a halogenated group, and R5 is an electron donating group.
  • the C end of the modified molecule contains an R3 group, which can be coupled with the surface of the carrier functional layer 3.
  • the surface of the carrier functional layer can have a hydroxyl group, and R3 can specifically be a hydroxyl group capable of bonding with a hydroxyl group.
  • the group for coupling; the R6 halogenated group and the R5 power supply group can realize ATRP reaction with the ligand molecule A of the quantum dot light-emitting layer 4 .
  • R3 includes one of the following:
  • R6 includes one of the following: -Cl; -Br; -I.
  • R5 includes one of the following: -O-; -S-.
  • R4 includes one of the following: -(CH 2 ) n2 -, wherein 1 ⁇ n2 ⁇ 12. R4 can make the modified molecule C have a certain length, which can play the role of co-solubilization.
  • the first reactant includes ligand molecule B, and the general formula of ligand molecule B is:
  • 1 ⁇ n3 ⁇ 12, 1 ⁇ m3 ⁇ 12, R9 is a group that coordinates with the quantum dot body
  • R11 is a group that forms a hydrogen bond with the intermediate substrate when transferring the quantum dot light-emitting layer.
  • the first reactant further includes a ligand molecule B
  • the ligand molecule B has a group R9 that can coordinate with the quantum dot body, so that one end can be connected to the quantum dot body, and the ligand molecule B can be connected to the transit substrate.
  • the hydrogen-bonded group R11 can then be combined with the intermediate substrate to stick the quantum dot light-emitting layer from the original carrier substrate.
  • the binding force of the covalent bond between the ligand molecule A of the quantum dot light-emitting layer and the carrier functional layer 3 through the ATRP reaction is greater than the hydrogen bond formed by the quantum dot light-emitting layer 4 through the ligand molecule B and the intermediate substrate.
  • the binding force of the quantum dot light-emitting layer 4 can be transferred from the intermediate substrate to the base substrate.
  • the binding force of the hydrogen bonds between the quantum dot light-emitting layer 4 and the intermediate substrate formed by the ligand molecules B is greater than the binding force of the quantum dot light-emitting layer 4 and the original carrier substrate, so that the quantum dot light-emitting layer 4 can be removed from the carrier.
  • the substrate is transferred to the transfer substrate.
  • R9 includes one of the following: -NH 2 ; -SH; -COOH.
  • R11 includes one of the following: -CHO; -OH; -COOH.
  • R7 includes one of the following: -O-; -N-; -C-; -S-.
  • R1 may be an atom connecting the main chain and the branched chain, and plays a role of connection.
  • R8 is a branched chain, which can make the ligand molecule B have a certain length and play the role of co-dissolution.
  • the R10 alkane or aromatic group can play a role of solubility aid.
  • the structure of the quantum dot body connected with the ligand molecule A can be specifically (that is, the structure formed after the quantum dot body is connected with the ligand molecule A):
  • the modified molecule C can be specifically:
  • the chain-initiated reaction that occurs on the surface of the quantum dot light-emitting layer 4 facing the carrier functional layer 3 is:
  • the structure of the quantum dot body connected with the ligand molecule A and the structure of the modified molecule C can cause the quantum dot light-emitting layer 4 and the carrier functional layer 3 to have the above chain-initiated reaction on the surface, and The following chain growth reaction occurs inside the quantum dot light-emitting layer 4 .
  • the structure of the molecular chain structure is: Among them, n4 ⁇ 1;
  • the chain growth reaction that occurs inside the quantum dot light-emitting layer is:
  • the material of the carrier functional layer 3 can be an inorganic metal oxide, and the surface of the inorganic metal oxide has hydroxyl groups, so that the modified molecule C can be bound to the surface of the carrier functional layer 3 .
  • the light emitting diode device in the embodiment of the present disclosure can be either an inverted structure or an upright structure.
  • the following is a specific example to illustrate:
  • the light emitting diode device is an inverted structure
  • the first electrode 2 is a cathode
  • the second electrode 5 is an anode
  • the carrier functional layer 3 is an electron transport layer
  • the material of the electron transport layer is zinc oxide
  • the light emitting diode device is an upright structure
  • the first electrode 2 is an anode
  • the second electrode 5 is a cathode
  • the carrier functional layer 3 is a hole transport layer
  • the material of the hole transport layer is nickel oxide.
  • an embodiment of the present disclosure further provides a display panel, which includes the light emitting diode device provided by the embodiment of the present disclosure.
  • the display panel further includes a thin film transistor, and the thin film transistor is electrically connected to the sub-light emitting device 80 .
  • the thin film transistors may be a-Si transistors, oxide transistors, or low temperature polysilicon transistors.
  • the thin film transistor may be a top gate thin film transistor or a bottom gate thin film transistor. As shown in FIG.
  • the thin film transistor includes a gate electrode 141 , an active layer 12 , a source and drain electrode layer 18 (specifically, it may include a source electrode 181 and a drain electrode 182 ), wherein the gate electrode 141 may be located on the backing liner of the active layer 12
  • the source-drain layer 18 is located on the side of the gate electrode 141 away from the active layer 12 , and is electrically connected to the sub-light emitting device 80 through the drain electrode 182 .
  • the display panel also includes a first storage capacitor electrode 142 and a second storage capacitor electrode 16, the first storage capacitor electrode 142 and the gate electrode 141 are provided in the same layer, and the second storage capacitor electrode 16 is provided separately, located between the gate electrode 141 and the source electrode 141. between the drain layers 18 .
  • a plurality of insulating layers may be disposed between the active layer 12 and the source and drain layers 18 , for example, the plurality of insulating layers include: a first insulating layer 13 disposed between the active layer 12 and the gate electrode 141 , the second insulating layer 15 is disposed between the gate electrode 141 and the second storage capacitor electrode 16 , and the interlayer dielectric layer 17 is disposed between the source-drain layer 18 and the second storage capacitor electrode 16 .
  • a passivation layer 191 may also be disposed between the source and drain layers 18 and the first electrode 2
  • a flat layer 192 may also be disposed between the passivation layer 191 and the first electrode 2 .
  • a buffer layer 11 may also be disposed between the base substrate 1 and the active layer 12 .
  • the light emitting diode device When the light emitting diode device is an inverted structure, there is a hole transport layer 61 between the quantum dot light emitting layer 4 and the second electrode 5, and a hole injection layer 62 between the hole transport layer 61 and the second electrode 5; the light emitting diode When the device is in an upright structure, there is an electron transport layer 61 between the quantum dot light-emitting layer 4 and the second electrode 5 , and an electron injection layer 62 between the electron transport layer 61 and the second electrode 5 .
  • an embodiment of the present disclosure further provides a display device, which includes the display panel provided by the embodiment of the present disclosure.
  • an embodiment of the present disclosure further provides a method for fabricating a light-emitting diode device, including:
  • Step S100 forming a quantum dot film layer including a first reactant on the carrier substrate, where the first reactant includes a quantum dot body, a ligand molecule A connected to the quantum dot body, and a ligand molecule B connected to the quantum dot body ;
  • the first reactant may be formed through a ligand exchange reaction, that is, the step S100 may include steps S101 and S102, as follows:
  • Step S101 forming an initial quantum dot film layer with initial ligands on a carrier substrate; specifically, in order to reduce the binding force between the initial quantum dot film layer and the carrier substrate, the carrier substrate may be treated first to reduce the subsequent The difficulty of transferring the dot film layer to the transfer substrate, that is, the step S101 may specifically include: treating the silicon-based substrate with octadecanetrimethoxysilicon; forming an initial quantum dot film with oleic acid ligands on the silicon-based substrate layer; wherein, the oleic acid ligand can be used as the initial ligand;
  • Step S102 forming a solution containing ligand molecule A and ligand molecule B on the carrier substrate on which the initial quantum dot film layer is formed, so that ligand molecule A, ligand molecule B and the initial ligand undergo a ligand exchange reaction;
  • ligand molecule A, ligand molecule B and the initial ligand undergo a ligand exchange reaction;
  • Step S200 contact the quantum dot film layer through the transfer substrate, so that the ligand molecules B in the first reactant form hydrogen bonds with the transfer substrate, and the quantum dot film layer is adhered; in the step S200, the first reactant can be made.
  • Ligand molecules B are pre-formed in the intermediate substrate, and then when the intermediate substrate is in contact with the quantum dot film layer on the carrier substrate with ligand molecules B, the ligand molecules B can form hydrogen bonds with the intermediate substrate, and the force of the hydrogen bonds is greater than The bonding force between the initial quantum dot film layer and the carrier substrate can further realize the adhesion of the quantum dot film layer from the carrier substrate;
  • Step S300 attaching the intermediate substrate with the quantum dot film layer to the base substrate formed with the modified molecules, so that the ligand molecule A of the first reactant on the surface of the quantum dot film layer performs atomic transfer radical transfer with the modified molecule.
  • a polymerization reaction is carried out, and a continuous atom transfer radical polymerization reaction is carried out inside the quantum dot film layer to form a quantum dot light-emitting layer, wherein the base substrate is formed with a first electrode and carriers located on the side of the first electrode away from the base substrate
  • the modified molecule is connected to the surface of the carrier functional layer away from the first electrode; in this step S300, in order to catalyze the ATRP reaction between the ligand molecule A and the modified molecule, the transit substrate with the quantum dot film layer is formed with the quantum dot film layer.
  • the substrate substrate of the modified molecule is bonded, the bonded transfer substrate and the substrate substrate can be immersed in anisole solution of cuprous chloride;
  • Step S400 removing the relay substrate; it should be noted that the ligand molecules B bound to the relay substrate can be specifically removed together with the relay substrate when the relay substrate is removed, that is, in the final light emitting diode device,
  • the molecular chain structure in the quantum dot light-emitting film layer may not contain the ligand molecule B, and the ligand molecule B exists in the process of fabricating the light-emitting diode device, and in the process of transferring the quantum dot film layer to the substrate; of course, Considering practical process limitations, the ligand molecule B may not be completely removed, and thus, the ligand molecule B may remain partially in the final light-emitting diode device.
  • Step S500 forming a second electrode.
  • a quantum dot film layer with weak bonding force with the carrier substrate is first formed on the carrier substrate, and then the intermediate substrate is contacted with the quantum dot film layer, so that the quantum dot film layer is formed. It forms a stronger hydrogen bond with the transfer substrate than with the carrier substrate.
  • the quantum dot film layer can be transferred along with the transfer substrate, and then the side of the transfer substrate with the quantum dot film layer is connected to the substrate.
  • the ligand molecule A in the quantum dot film layer and the modified molecule C of the substrate substrate can undergo ATRP reaction.
  • the covalent bond formed by the ATRP reaction has a stronger binding force than the hydrogen bond, which can be used to transfer the substrate.
  • the quantum dot film layer can be left on the base substrate, so that the quantum dot film layer can be formed on the base substrate by transfer method.
  • the first reactant of the quantum dot film layer can be mixed with the modified molecules of the base substrate, at the interface between the quantum dot film layer and the carrier functional layer, and inside the quantum dot film layer.
  • the ATRP reaction occurs, so that the quantum dot film layer forms a tightly integrated whole, which can be transferred from the intermediate substrate to the base substrate together, achieving high transfer yield of the quantum dot film layer, and avoiding the transfer of only part of the quantum dot film layer from the intermediate substrate. to the substrate substrate problem.
  • the manufacturing method further includes:
  • Step S600 providing a base substrate
  • Step S700 forming a carrier functional layer on one side of the base substrate
  • Step S800 forming a solution containing modified molecules on the surface of the carrier functional layer, so as to couple the modified molecules with the hydroxyl groups on the surface of the carrier functional layer.
  • the manufacturing method further includes:
  • Step S900 contacting the intermediate substrate with the quantum dot film layer bonded to the gravure plate with grooves to form a patterned quantum dot film layer.
  • a quantum dot film layer that is raised at positions corresponding to the grooves that is, the quantum dots outside the positions corresponding to the grooves
  • the dots are left in the gravure.
  • the intermediate substrate After contacting with the gravure, the intermediate substrate only has a quantum dot film layer at the position corresponding to the groove).
  • the convex quantum dot film can be The dot film layer is combined with the display substrate in the recessed area where the light emitting device is located, so that the patterned quantum dot film layer is formed in the light emitting device area defined by the retaining wall 7 .
  • FIG. 7 is only a schematic illustration of the transfer using the groove of the gravure as a ring.
  • the shape of the groove of the gravure can be consistent with the pattern of the area where the light-emitting device of the display substrate is located. The above is the method of forming patterned quantum dots through a gravure plate with grooves.
  • the substrate Before the intermediary substrate is in contact with the gravure plate, it is a flat structure of a whole layer.
  • the substrate has convex parts and concave parts), when the transfer substrate contacts the carrier substrate of the original substrate, it can contact the quantum dot film layer on the carrier substrate (that is, the convex part of the transfer substrate).
  • the substrate and the quantum dot film layer form hydrogen bonds, and the quantum dot film layer can be adsorbed by the transfer substrate, but there is no position in contact with the quantum dot film layer (that is, the concave part of the transfer substrate), and the quantum dot film layer will not be adsorbed.
  • a patterned quantum dot film layer is formed on the transfer substrate, and then the transfer substrate can be directly contacted with the display substrate to transfer the patterned quantum dot film layer to the display substrate.
  • the transfer substrate The pattern can be consistent with the pattern of the area where the light-emitting device of the display substrate is located.
  • the material of the relay substrate may be polydimethylsiloxane (PDMS).
  • the relay substrate is in contact with the quantum dot film layer, which may specifically include: the material is polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • the substrate of methyl siloxane is in contact with the quantum dot film layer.
  • the material of the intermediate substrate is PDMS, which can form hydrogen bonds with the ligand molecules B in the quantum dot film layer.
  • patterned quantum dot film layer spin-coat 15mg/ml quantum dot solution (rotation speed 2500rpm/s) on the silicon-based substrate (carrier substrate) treated with octadecanetrimethoxysilicon, after spin-coating, use The methanol solution of ligand molecule A and ligand molecule B (concentration 20mg/ml) was dropped on the quantum dot film layer for ligand exchange, and after standing for 30s, the methanol was removed, and methanol was used to remove the excess ligand on the surface of the quantum dot film layer. After two cleanings, anneal at 120°C for 20 minutes; use the PDMS substrate (intermediate substrate) to quickly stick the quantum dot film layer, and contact it with the gravure groove to form a patterned quantum dot film layer;
  • the ITO substrate (substrate) was first spin-coated with 15 mg/ml zinc oxide (as the carrier functional layer formed later) nanoparticle solution (rotation speed 4000 rpm/s), and annealed at 120°C for 20 minutes. Place the modified molecule C ethanol solution on the zinc oxide film for 5 minutes, then spin off the excess solvent, and anneal at 100 degrees for 10 minutes to accelerate the coupling of the silane reagent and the hydroxyl group on the surface of zinc oxide; pattern the PDMS substrate (transit substrate)
  • the quantum dot film layer is in contact with the surface of the zinc oxide film and is immersed in anisole solution containing cuprous chloride, and conducts ATRP reaction at 80 degrees in an anhydrous and oxygen-free nitrogen atmosphere.
  • the reaction is completed, it is removed by washing with anisole. Usually with impurities, annealed at 120 degrees for 20 minutes; then, the hole transport layer material and the silver electrode (second electrode) were evaporated over the quantum dot film layer to prepare a patterned quantum dot light-emitting diode device.

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Abstract

一种发光二极管器件、显示面板、显示装置和制作方法，所述发光二极管器件包括：衬底基板（1）；第一电极（2），位于所述衬底基板（1）的一侧；载流子功能层（3），位于所述第一电极（2）的背离所述衬底基板（1）的一侧；量子点发光层（4），位于所述载流子功能层（3）的背离所述第一电极（2）的一侧，所述量子点发光层（4）内部具有分子链结构，其中，所述分子链结构由第一反应物和修饰分子发生原子转移自由基聚合反应形成，所述第一反应物通过配体分子A与所述修饰分子发生原子转移自由基聚合反应，所述修饰分子初始状态为连接于所述载流子功能层（3）面向所述量子点发光层（4）的一面；第二电极（5），位于所述量子点发光层（4）的背离所述载流子功能层（3）的一侧。

Description

发光二极管器件、显示面板、显示装置和制作方法 技术领域
本发明涉及半导体技术领域，尤其涉及一种发光二极管器件、显示面板、显示装置和制作方法。
背景技术
随着纳米科学技术的不断发展与演变，制备出具有特定图案化结构的纳米材料逐渐成为现代纳米科学技术研究领域中一个日益重要的研究方向。作为一种新型的纳米材料——量子点，一经出现，就因诸多优点引起了广大研究学者的热切关注。而具有特定图案化的量子点层的成功制备更是在扩大其应用范围的同时，掀起了纳米界又一波的研究热潮。量子点发光二极管显示器(Quantum Dots Light Emitting Doide Display,QLED)是基于有机发光显示器的基础上发展起来的一种新型显示技术。而两者存在的区别是QLED里的发光层为量子点层，它的原理是电子/空穴通过电子/空穴传输层注入到量子点层，电子和空穴在量子点层中复合发光。与有机发光二极管显示器件相比，QLED具有发光峰窄，色彩饱和度高，色域宽等优点。
发明内容
本公开实施例提供一种发光二极管器件，其中，包括：
衬底基板；
第一电极，位于所述衬底基板的一侧；
载流子功能层，位于所述第一电极的背离所述衬底基板的一侧；
量子点发光层，位于所述载流子功能层的背离所述第一电极的一侧，所述量子点发光层内部具有分子链结构，其中，所述分子链结构由第一反应物和修饰分子发生原子转移自由基聚合反应形成，所述第一反应物包括量子点本体和连接于所述量子点本体的配体分子A，所述第一反应物通过所述配体 分子A与所述修饰分子发生原子转移自由基聚合反应，所述修饰分子初始状态为连接于所述载流子功能层面向所述量子点发光层的一面；
第二电极，位于所述量子点发光层的背离所述载流子功能层的一侧。
在一种可能的实施方式中，所述配体分子A的通式为：
Figure PCTCN2020110338-appb-000001
其中，R1为供电子基团，R2为助溶基团。
在一种可能的实施方式中，R1包括以下之一：
Figure PCTCN2020110338-appb-000002
-S-。
在一种可能的实施方式中，R2包括以下之一：
-(CH 2) n1-；
Figure PCTCN2020110338-appb-000003
其中，1≤n1≤8，1≤m1≤8。
在一种可能的实施方式中，所述修饰分子的通式为：
Figure PCTCN2020110338-appb-000004
其中，R3为与所述载流子功能层表面发生偶联的基团，R6为卤代基团，R5为供电子基团。
在一种可能的实施方式中，R3包括以下之一：
Figure PCTCN2020110338-appb-000005
在一种可能的实施方式中，R6包括以下之一：
-Cl；
-Br；
-I。
在一种可能的实施方式中，R5包括以下之一：
Figure PCTCN2020110338-appb-000006
-O-；
Figure PCTCN2020110338-appb-000007
-S-。
在一种可能的实施方式中，R4包括以下之一：
-(CH 2) n2-，其中，1≤n2≤12。
在一种可能的实施方式中，所述第一反应物包括配体分子B，所述配体分子B的通式为：
Figure PCTCN2020110338-appb-000008
其中，1≤n3≤12，1≤m3≤12，R9为与所述量子点本体进行配位的基团，R11为转印所述量子点发光层时与中转基板形成氢键的基团。
在一种可能的实施方式中，R9包括以下之一：
-NH 2；
-SH；
-COOH。
在一种可能的实施方式中，R11包括以下之一：
-CHO；
-OH；
-COOH。
在一种可能的实施方式中，R7包括以下之一：
-O-；
-N-；
-C-；
-S-。
在一种可能的实施方式中，R8包括以下之一：
-(CH 2) a-，其中，a＝1、2、3或4。
在一种可能的实施方式中，R10包括以下之一：
-(CH 2) b-；
Figure PCTCN2020110338-appb-000009
其中，1≤b≤8，c＝1或2。
在一种可能的实施方式中，连接有所述配体分子A的所述量子点本体的结构为：
Figure PCTCN2020110338-appb-000010
所述修饰分子为：
Figure PCTCN2020110338-appb-000011
所述量子点发光层的面向所述载流子功能层的表面发生的链引发反应为：
Figure PCTCN2020110338-appb-000012
在一种可能的实施方式中，所述分子链结构的结构为：
Figure PCTCN2020110338-appb-000013
其中，n4≥1；
所述量子点发光层的内部发生的链增长反应为：
Figure PCTCN2020110338-appb-000014
在一种可能的实施方式中，所述载流子功能层的材料为无机金属氧化物，所述无机金属氧化物的表面具有羟基。
在一种可能的实施方式中，所述第一电极为阴极，所述第二电极为阳极，所述载流子功能层为电子传输层，所述电子传输层的材料为氧化锌；
或者，所述第一电极为阳极，所述第二电极为阴极，所述载流子功能层为空穴传输层，所述空穴传输层的材料为氧化镍。
本公开实施例还提供一种显示面板，其中，包括如本公开实施例提供的所述发光二极管器件。
本公开实施例还提供一种显示装置，其中，包括如本公开实施例提供的所述显示面板。
本公开实施例还提供一种发光二极管器件的制作方法，其中，包括：
在载体基板上形成包括第一反应物的量子点膜层，所述第一反应物包括量子点本体，与所述量子点本体连接的配体分子A，以及与所述量子点本体连接的配体分子B；
通过中转基板与所述量子点膜层接触，以使所述第一反应物中的所述配体分子B与所述中转基板形成氢键，粘起所述量子点膜层；
将具有所述量子点膜层的所述中转基板与形成有修饰分子的衬底基板进行贴合，以使所述量子点膜层表面所述第一反应物的所述配体分子A，与所述修饰分子进行原子转移自由基聚合反应，并在所述量子点膜层内部进行持续原子转移自由基聚合反应，形成量子点发光层，其中，所述衬底基板形成有第一电极以及位于所述第一电极背离所述衬底基板一侧的载流子功能层，所述修饰分子连接于所述载流子功能层的背离所述第一电极的表面；
移去所述中转基板；
形成第二电极。
在一种可能的实施方式中，所述在载体基板上形成包括第一反应物的量子点膜层，包括：
在载体基板上形成具有初始配体的初始量子点膜层；
在形成有所述初始量子点膜层的所述载体基板形成含有配体分子A和配体分子B的溶液，以使所述配体分子A、所述配体分子B与所述初始配体发生配体交换反应。
在一种可能的实施方式中，所述在载体基板上形成具有初始配体的初始量子点膜层，包括：
采用十八烷三甲氧基硅处理硅基基板；
在所述硅基基板上形成具有油酸配体的初始量子点膜层。
在一种可能的实施方式中，在将具有量子点膜层的所述中转基板与形成有修饰分子的载流子功能层的衬底基板进行贴合之前，所述制作方法还包括：
提供一衬底基板；
在所述衬底基板的一侧形成载流子功能层；
在所述载流子功能层的表面形成含有所述修饰分子的溶液，以使所述修饰分子与所述载流子功能层表面的羟基偶联。
在一种可能的实施方式中，在粘起所述量子点膜层之后，以及在将具有所述量子点膜层的所述中转基板与形成有修饰分子的衬底基板进行贴合之前，所述制作方法还包括：
将粘接有所述量子点膜层的所述中转基板与具有沟槽的凹版接触，形成图案化的量子点膜层。
在一种可能的实施方式中，在将具有所述量子点膜层的所述中转基板与形成有修饰分子的衬底基板进行贴合时，所述制作方法还包括：
浸泡在氯化亚铜的苯甲醚溶液中。
在一种可能的实施方式中，所述通过中转基板与所述量子点膜层接触，包括：
通过材料为聚二甲基硅氧烷的基板与所述量子点膜层接触。
附图说明
图1为本公开实施例提供的一种发光二极管器件的结构示意图；
图2为本公开实施例提供的量子点膜层的配体与衬底基板的修饰分子C结合的示意图；
图3为本公开实施例提供的一种发光二极管器件的制作流程示意图；
图4为本公开实施例提供的一种发光二极管器件的制作流程示意图；
图5为本公开实施例提供的一种具体的发光二极管器件的制作流程示意图；
图6为本公开实施例提供的一种形成图案化量子点膜层的发光二极管器件的制作流程示意图；
图7为本公开实施例提供的一种具体的量子点膜层的转移流程示意图。
具体实施方式
为了使得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。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“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。“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。“上”、“下”、“左”、“右”等仅用于表示相对位置关系，当被描述对象的绝对位置改变后，则该相对位置关系也可能相应地改变。
为了保持本公开实施例的以下说明清楚且简明，本公开省略了已知功能和已知部件的详细说明。
参见图1，本公开实施例提供一种发光二极管器件，其中，包括：
衬底基板1；
第一电极2，位于衬底基板1的一侧，具体的，第一电极2可以为多个相互间隔的结构；
载流子功能层3，位于第一电极2的背离衬底基板1的一侧，具体的，载流子功能层3可以为多个相互间隔且与第一电极2一一对应的结构，第一电极2在衬底基板1的正投影可以覆盖对应的载流子功能层3在衬底基板的正投影；具体的，发光二极管器件还可以具有挡墙7，挡墙7用于间隔出光颜色不同的子发光器件80(如图1所示，可以包括两个子发光器件80，分别位于 左侧的子发光器件80和位于右侧的子发光器件80，每一子发光器件80包括第一电极2、载流子功能层3、量子点发光层4、第二电极5，当然，图1仅是以发光二极管器件具有两个子发光器件80进行的举例说明，在具体实施时，发光二极管器件可以具有更多个子发光器件80，本公开实施例不以此为限)。
量子点发光层4，位于载流子功能层3的背离第一电极2的一侧，量子点发光层4内部具有分子链结构X，其中，分子链结构X由第一反应物和修饰分子C发生原子转移自由基聚合反应(Atom Transfer Radical Polymerization，ATRP)形成，结合图2所示，其中PDMS(聚二甲基硅氧烷(polydimethylsiloxane，PDMS))为转印量子点发光层时所使用的中转基板，ZnO作为载流子功能层3的材料，ITO(氧化铟锡)作为第一电极2的材料，第一反应物包括量子点本体QD和连接于量子点本体QD的配体分子A，第一反应物通过配体分子A与修饰分子C发生原子转移自由基聚合反应，修饰分子C初始状态为连接于载流子功能层3面向量子点发光层4的一面，也即，在未进行原子转移自由基聚合反应时，可以先在载流子功能层3的面向量子点发光层4的表面形成修饰分子C，而量子点发光层3为具有第一反应物的膜层，在通过转印量子点发光层的方式，使载流子功能层3与量子点发光层4接触时，由于第一反应物中的配体分子A可以与修饰分子C发生原子转移自由基聚合反应，进而可以先使量子点发光层3表面的第一反应物与修饰分子C结合在一起，随着原子转移自由基聚合反应的进一步发生，量子点发光层3内部的第一反应物也通过反应形成分子链结构，使整个量子点发光层3形成具有由分子链结构X相互结合在一体的整体结构；量子点本体可以为常规的量子点发光材料；
第二电极5，位于量子点发光层4的背离载流子功能层3的一侧，具体的，第二电极5可以为一整层结构。当然，第二电极5也可以为相互间隔的结构。
本公开实施例提供的发光二极管器件，量子点发光层4内部具有经第一反应物和修饰分子C经原子转移自由基聚合反应形成的分子链结构X，即，量子点发光层4的面向载流子功能层3的第一表面41，量子点发光层4的面向第二电极5的第二表面42，以及第一表面41和第二表面42之间的区域均 具有分子链结构X，整个量子点发光层4整体均形成由分子链结构X相互结合在一起的整体结构，在通过转印方式利用中转基板将该量子点发光层4由原始的载体基板转印到发光二极管器件的衬底基板1上时，该量子点发光层4可以作为一个整体的结构，从中转基板一起转印到衬底基板1，改善现有技术的量子点发光层4仅具有量子点本体时，仅能将中转基板表面的部分量子点发光层转印到衬底基板，致使发光二极管器件的转印良率较低的问题。
在具体实施时，配体分子A的结构特征为含有苯乙烯及其衍生物，丙烯酸酯及其衍生物，丙烯酰胺及其衍生物和丙烯晴等。具体的，配体分子A的通式为：
Figure PCTCN2020110338-appb-000015
其中，R1为供电子基团，R2为助溶基团。本公开实施例中，配体分子A为
Figure PCTCN2020110338-appb-000016
可以通过R1为进行ATRP反应提供电子，有利于ATRP反应的进行，R2可以增加溶解性，有利于配体分子A制作于量子点本体QD上。具体的，可以是配体分子A中除R2以外的结构为含有苯乙烯及其衍生物，丙烯酸酯及其衍生物，丙烯酰胺及其衍生物和丙烯晴等。
具体的，R1可以包括以下之一：
Figure PCTCN2020110338-appb-000017
-S-。
具体的，R2包括以下之一：-(CH 2) n1-；
Figure PCTCN2020110338-appb-000018
其中，1≤n1≤8，1≤m1≤8。
在具体实施时，修饰分子C的通式为：
Figure PCTCN2020110338-appb-000019
其中，R3为与载流子功能层表面发生偶联的基团，R6为卤代基团，R5为供电子基团。本公开实施例中，修饰分子C一端含有R3基团，可以与载流子功能层3的表面进行偶联，具体的，载流子功能层的表面可以具有羟基，R3具体可以 是能与羟基进行偶联的基团；具有的R6卤代基团，以及R5供电基团，可以实现与量子点发光层4的配体分子A进行ATRP反应。
具体的，R3包括以下之一：
Figure PCTCN2020110338-appb-000020
具体的，R6包括以下之一：-Cl；-Br；-I。
具体的，R5包括以下之一：
Figure PCTCN2020110338-appb-000021
-O-；
Figure PCTCN2020110338-appb-000022
-S-。
具体的，R4包括以下之一：-(CH 2) n2-，其中，1≤n2≤12。R4可以使修饰分子C具有一定长度，可以起到助溶的作用。
在具体实施时，第一反应物包括配体分子B，配体分子B的通式为：
Figure PCTCN2020110338-appb-000023
其中，1≤n3≤12，1≤m3≤12，R9为与量子点本体进行配位的基团，R11为转印量子点发光层时与中转基板形成氢键的基团。本公开实施例中，第一反应物还包括配体分子B，配体分子B具有可以与量子点本体进行配位的基团R9，进而可以实现一端与量子点本体连接，以及具有与中转基板形成氢键的基团R11，进而可以实现与中转基板结合，将量子点发光层从原始的载体基板黏起。需要说明的是，量子点发光层的配体分子A与载流子功能层3通过ATRP反应的共价键的结合力，大于量子点发光层4通过配体分子B与中转基板形成的氢键的结合力，进而可以实现将量子点发光层4从中转基板转移到 衬底基板。另外，量子点发光层4通过配体分子B与中转基板形成的氢键的结合力，要大于量子点发光层4与原始的载体基板的结合力，进而可以实现将量子点发光层4从载体基板转移至中转基板。
具体的，R9包括以下之一：-NH 2；-SH；-COOH。
具体的，R11包括以下之一：-CHO；-OH；-COOH。
具体的，R7包括以下之一：-O-；-N-；-C-；-S-。本公开实施例中，R1可以为连接主链和支链的原子，起到连接的作用。
具体的，R8包括以下之一：-(CH 2) a-，其中，a＝1、2、3、或4。本公开实施例中，R8为支链，可以使配体分子B具有一定长度，起到助溶的作用。
具体的，R10包括以下之一：-(CH 2) b-；
Figure PCTCN2020110338-appb-000024
其中，1≤b≤8，c＝1或2。本公开实施例中，R10烷烃或者芳香基团，可以起到助溶的作用。
在具体实施时，连接有配体分子A的量子点本体的结构具体可以为(即量子点本体与配体分子A连接后形成的结构)：
Figure PCTCN2020110338-appb-000025
修饰分子C具体可以为：
Figure PCTCN2020110338-appb-000026
量子点发光层4的面向载流子功能层3的表面发生的链引发反应为：
Figure PCTCN2020110338-appb-000027
本公开实施例中，连接有配体分子A的量子点本体的结构，以及修饰分子C的结构，可以使量子点发光层4与载流子功能层3在表面发生如上的链引发反应，以及在量子点发光层4内部发生如下的链增长反应。
具体的，分子链结构的结构为:
Figure PCTCN2020110338-appb-000028
其中，n4≥1；
量子点发光层的内部发生的链增长反应为：
Figure PCTCN2020110338-appb-000029
在具体实施时，载流子功能层3的材料可以为无机金属氧化物，无机金属氧化物的表面具有羟基，如此可以使修饰分子C结合到载流子功能层3的表面。
在具体实施时，结合图1所示，本公开实施例中的发光二极管器件既可以为倒置结构，也可以为正置结构，以下进行具体举例说明：
例如，发光二极管器件为倒置结构，第一电极2为阴极，第二电极5为阳极，载流子功能层3为电子传输层，电子传输层的材料为氧化锌；
又例如，发光二极管器件为正置结构，第一电极2为阳极，第二电极5为阴极，载流子功能层3为空穴传输层，空穴传输层的材料为氧化镍。
基于同一发明构思，本公开实施例还提供一种显示面板，其中，包括如本公开实施例提供的发光二极管器件。
在具体实施时，显示面板还包括薄膜晶体管，薄膜晶体管与子发光器件80电连接。薄膜晶体管可以为a-Si晶体管、氧化物晶体管、或低温多晶硅晶体管。薄膜晶体管可以为顶栅薄膜晶体管、底栅薄膜晶体管。结合图3所示，薄膜晶体管包括栅极141、有源层12、源漏极层18(具体可以包括源极181以及漏极182)，其中，栅极141可以位于有源层12的背离衬底基板1的一侧，源漏极层18位于栅极141的背离有源层12的一侧，通过漏极182与子发光器件80电连接。进一步的，显示面板还包括第一存储电容电极142和第二存储电容电极16，第一存储电容电极142与栅极141同层设置，第二存储电容电极16单独设置，位于栅极141与源漏极层18之间。进一步的，有源层12与源漏极层18之间还可以设置有多个绝缘层，例如，多个绝缘层包括：设置于有源层12与栅极141之间的第一绝缘层13，设置于栅极141与第二存储电容电极16之间的第二绝缘层15，设置于源漏极层18与第二存储电容电极16之间的层间介质层17。进一步的，源漏极层18与第一电极2之间还可以设置有钝化层191，钝化层191与第一电极2之间还可以设置有平坦层192。进一步的，衬底基板1与有源层12之间还可以设置有缓冲层11。
发光二极管器件为倒置结构时，量子点发光层4与第二电极5之间还具有空穴传输层61，空穴传输层61与第二电极5之间还具有空穴注入层62；发光二极管器件为正置结构时，量子点发光层4与第二电极5之间还具有电子传输层61，电子传输层61与第二电极5之间还具有电子注入层62。
基于同一发明构思，本公开实施例还提供一种显示装置，其中，包括如本公开实施例提供的显示面板。
参见图4所示，本公开实施例还提供一种发光二极管器件的制作方法，其中，包括：
步骤S100、在载体基板上形成包括第一反应物的量子点膜层，第一反应物包括量子点本体，与量子点本体连接的配体分子A，以及与量子点本体连接的配体分子B；
具体的，可以通过配体交换反应形成第一反应物，即，该S100步骤，可以包括步骤S101和步骤S102，如下：
步骤S101、在载体基板上形成具有初始配体的初始量子点膜层；具体的，为了降低初始量子点膜层与载体基板的结合力，可以先对载体基板进行处理，以降低后续将初始量子点膜层转印到中转基板时的难度，即，该S101步骤具体可以包括：采用十八烷三甲氧基硅处理硅基基板；在硅基基板上形成具有油酸配体的初始量子点膜层；其中，油酸配体可以作为初始配体；
步骤S102、在形成有初始量子点膜层的载体基板形成含有配体分子A和配体分子B的溶液，以使配体分子A、配体分子B与初始配体发生配体交换反应；配体分子A和配体分子B的具体材料，可以参见本发明实施例提供的发光二极管器件实施例给出的具体材料；
步骤S200、通过中转基板与量子点膜层接触，以使第一反应物中的配体分子B与中转基板形成氢键，粘起量子点膜层；该S200步骤中，可以使第一反应物中预先形成配体分子B，进而在中转基板与具有配体分子B的载体基板上的量子点膜层接触时，配体分子B可以与中转基板形成氢键，而氢键的作用力要大于初始量子点膜层与载体基板之间的结合力，进而可以实现将量子点膜层从载体基板上粘起；
步骤S300、将具有量子点膜层的中转基板与形成有修饰分子的衬底基板进行贴合，以使量子点膜层表面第一反应物的配体分子A，与修饰分子进行原子转移自由基聚合反应，并在量子点膜层内部进行持续原子转移自由基聚 合反应，形成量子点发光层，其中，衬底基板形成有第一电极以及位于第一电极背离衬底基板一侧的载流子功能层，修饰分子连接于载流子功能层的背离第一电极的表面；该步骤S300中，为了催化配体分子A与修饰分子发生ATRP反应，将具有量子点膜层的中转基板与形成有修饰分子的衬底基板进行贴合时，可以将贴合的中转基板和衬底基板浸泡在氯化亚铜的苯甲醚溶液中；
步骤S400、移去中转基板；需要说明的是，与中转基板结合的配体分子B，在移去中转基板时，具体可随中转基板一并被去除，即，在最终的发光二极管器件中，量子点发光膜层中的分子链结构可以不含有配体分子B，配体分子B存在于对发光二极管器件制作过程中，在将量子点膜层转印到衬底基板的过程中；当然，考虑到实际工艺限制，配体分子B可能不能被完全去除，因此，在最终的发光二极管器件中，配体分子B可能会残留部分。
步骤S500、形成第二电极。
本公开实施例提供的发光二极管器件的制作方法，先在载体基板上形成与载体基板的结合力较弱的量子点膜层，再将中转基板与量子点膜层接触，以使量子点膜层与中转基板形成较与载体基板结合力更强的氢键，在将中转基板移走时，可以使量子点膜层随中转基板一起转移走，再将中转基板有量子点膜层的一面与衬底基板贴合时，可以使量子点膜层中的配体分子A与衬底基板的修饰分子C进行ATRP反应，因ATRP反应形成的共价键的结合力大于氢键，进而可以在将中转基板与衬底基板分离时，可以将量子点膜层留在衬底基板，实现在衬底基板上通过转印方式形成量子点膜层，而且，相比于现有技术转印量子点膜层的方式，本公开实施例提供的制作方法，量子点膜层的第一反应物可以和衬底基板的修饰分子，在量子点膜层与载流子功能层的界面，以及量子点膜层内部均发生ATRP反应，使量子点膜层形成一个紧密结合的整体，可以一起从中转基板转移到衬底基板，实现量子点膜层的高转移良率，避免仅有部分量子点膜层从中转基板转移到衬底基板的问题。
在具体实施时，结合图5所示，在将具有量子点膜层的中转基板与形成有修饰分子的载流子功能层的衬底基板进行贴合之前，制作方法还包括：
步骤S600、提供一衬底基板；
步骤S700、在衬底基板的一侧形成载流子功能层；
步骤S800、在载流子功能层的表面形成含有修饰分子的溶液，以使修饰分子与载流子功能层表面的羟基偶联。
在具体实施时，参见图6所示，为了形成图案化的量子点膜层，可以在步骤S200之后，以及在步骤S300之前，即，在粘起量子点膜层之后，以及在将具有量子点膜层的中转基板与形成有修饰分子的衬底基板进行贴合之前，制作方法还包括：
步骤S900、将粘接有量子点膜层的中转基板与具有沟槽的凹版接触，形成图案化的量子点膜层。结合图7所示，中转基板与具有沟槽的凹版接触后，可以在中转基板上形成在与沟槽对应位置处为凸起的量子点膜层(即，与沟槽区对应位置以外的量子点留在了凹版，与凹版接触后，中转基板仅在与沟槽对应位置处有量子点膜层)，在将具有凸起的量子点膜层转移到显示基板时，可以使凸起的量子点膜层与显示基板在发光器件所在的区域为凹陷的区域进行对合，实现将图案化的量子点膜层形成在由挡墙7界定的发光器件区域内。当然，需要说明的是，图7仅是以凹版的沟槽为圆环进行的转移示意说明，在具体实施时，凹版的沟槽形状可以与显示基板的发光器件所在区域图案一致。以上为通过具有沟槽的凹版形成图案化量子点的方式，中转基板在与凹版接触之前为一整层的平坦结构，在具体实施时，也可以是通过形成图案化的中转基板(即，中转基板有凸起的部分，也有凹陷的部分)，中转基板与原始基板的载体基板接触时，能与载体基板上的量子点膜层接触的位置(也即中转基板的凸起部分)，因中转基板与量子点膜层形成氢键，量子点膜层可以被中转基板吸附起，而没有与量子点膜层接触的位置(也即中转基板的凹陷部分)，不会吸附起量子点膜层，进而实现在中转基板上形成图案化的量子点膜层，之后，可以将该中转基板直接与显示基板接触，实现将图案化的量子点膜层转移到显示基板上，该种转移方式，中转基板的图案可以与显示基板的发光器件所在区域图案一致。
在具体实施时，中转基板的材质具体可以为聚二甲基硅氧烷(polydimethylsiloxane，PDMS)，对于步骤S200中的，通过中转基板与量子点膜层接触，具体可以包括：通过材料为聚二甲基硅氧烷的基板与量子点膜层接触。中转基板的材质为PDMS，可以与量子点膜层中的配体分子B形成氢键。
为了更清楚地理解本公开实施例提供的发光二极管器件的制作方法，结合图7所示，以下以发光二极管器件为倒置结构进行具体举例说明如下：
图案化量子点膜层的制备：在十八烷三甲氧基硅处理过的硅基基板(载体基板)上旋涂15mg/ml的量子点溶液(转速2500rpm/s)，旋涂完成后，使用配体分子A和配体分子B的甲醇溶液(浓度20mg/ml)滴在量子点膜层上进行配体交换，静置30s后旋去甲醇，使用甲醇对量子点膜层表面多余配体进行两次清洗后，120℃退火20分钟；用PDMS基板(中转基板)快速的粘起量子点膜层，将其与凹版沟槽接触，形成图案化的量子点膜层；
在ITO基板(衬底基板)首先旋涂15mg/ml的氧化锌(作为后续形成的载流子功能层)纳米粒子溶液(转速4000rpm/s)，120℃退火20分钟。将修饰分子C乙醇溶液置于氧化锌薄膜之上5分钟，之后旋掉多余溶剂，100度退火10分钟，加速硅烷试剂和氧化锌表面羟基的偶联；将PDMS基板(中转基板)上图形化的量子点膜层与氧化锌薄膜表面接触并浸泡在含有氯化亚铜的苯甲醚溶液中，在无水无氧的氮气氛围中80度进行ATRP反应，反应完成后通过苯甲醚洗涤除去多以杂质，120度退火20分钟；接着，在量子点膜层上方蒸镀空穴传输层材料和银电极(第二电极)，制备图案化的量子点发光二极管器件。
尽管已描述了本发明的优选实施例，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发明范围的所有变更和修改。
显然，本领域的技术人员可以对本发明实施例进行各种改动和变型而不脱离本发明实施例的精神和范围。这样，倘若本发明实施例的这些修改和变 型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。

Claims (28)

  1. 一种发光二极管器件，其中，包括：
    衬底基板；
    第一电极，位于所述衬底基板的一侧；
    载流子功能层，位于所述第一电极的背离所述衬底基板的一侧；
    量子点发光层，位于所述载流子功能层的背离所述第一电极的一侧，所述量子点发光层内部具有分子链结构，其中，所述分子链结构由第一反应物和修饰分子发生原子转移自由基聚合反应形成，所述第一反应物包括量子点本体和连接于所述量子点本体的配体分子A，所述第一反应物通过所述配体分子A与所述修饰分子发生原子转移自由基聚合反应，所述修饰分子初始状态为连接于所述载流子功能层面向所述量子点发光层的一面；
    第二电极，位于所述量子点发光层的背离所述载流子功能层的一侧。
  2. 如权利要求1所述的发光二极管器件，其中，所述配体分子A的通式为：
    Figure PCTCN2020110338-appb-100001
    其中，R1为供电子基团，R2为助溶基团。
  3. 如权利要求2所述的发光二极管器件，其中，R1包括以下之一：
    Figure PCTCN2020110338-appb-100002
    -S-
    。
  4. 如权利要求3所述的发光二极管器件，其中，R2包括以下之一：
    -(CH 2) n1-
    ；
    Figure PCTCN2020110338-appb-100003
    其中，1≤n1≤8，1≤m1≤8。
  5. 如权利要求1所述的发光二极管器件，其中，所述修饰分子的通式为：
    Figure PCTCN2020110338-appb-100004
    其中，R3为与所述载流子功能层表面发生偶联的基团，R6为卤代基团，R5为供电子基团。
  6. 如权利要求5所述的发光二极管器件，其中，R3包括以下之一：
    Figure PCTCN2020110338-appb-100005
  7. 如权利要求5所述的发光二极管器件，其中，R6包括以下之一：
    -Cl；
    -Br；
    -I。
  8. 如权利要求5所述的发光二极管器件，其中，R5包括以下之一：
    Figure PCTCN2020110338-appb-100006
    -O-
    ；
    Figure PCTCN2020110338-appb-100007
    -S-
    。
  9. 如权利要求5所述的发光二极管器件，其中，R4包括以下之一：
    -(CH 2) n2-，其中，1≤n2≤12。
  10. 如权利要求1所述的发光二极管器件，其中，所述第一反应物包括配体分子B，所述配体分子B的通式为：
    Figure PCTCN2020110338-appb-100008
    其中，1≤n3≤12，1≤m3≤12，R9为与所述量子点本体进行配位的基团，R11为转印所述量子点发光层时与中转基板形成氢键的基团。
  11. 如权利要求10所述的发光二极管器件，其中，R9包括以下之一：
    -NH 2；
    -SH；
    -COOH。
  12. 如权利要求10所述的发光二极管器件，其中，R11包括以下之一：
    -CHO；
    -OH；
    -COOH。
  13. 如权利要求10所述的发光二极管器件，其中，R7包括以下之一：
    -O-；
    -N-；
    -C-；
    -S-。
  14. 如权利要求10所述的发光二极管器件，其中，R8包括以下之一：
    -(CH 2) a-，其中，a＝1、2、3或4。
  15. 如权利要求10所述的发光二极管器件，其中，R10包括以下之一：
    -(CH 2) b-；
    Figure PCTCN2020110338-appb-100009
    其中，1≤b≤8，c＝1或2。
  16. 如权利要求5所述的发光二极管器件，其中，连接有所述配体分子A的所述量子点本体的结构为：
    Figure PCTCN2020110338-appb-100010
    所述修饰分子为：
    Figure PCTCN2020110338-appb-100011
    所述量子点发光层的面向所述载流子功能层的表面发生的链引发反应为：
    Figure PCTCN2020110338-appb-100012
  17. 如权利要求16所述的发光二极管器件，其中，所述分子链结构为:
    Figure PCTCN2020110338-appb-100013
    其中，n4≥1；
    所述量子点发光层的内部发生的链增长反应为：
    Figure PCTCN2020110338-appb-100014
  18. 如权利要求1所述的发光二极管器件，其中，所述载流子功能层的材料为无机金属氧化物，所述无机金属氧化物的表面具有羟基。
  19. 如权利要求18所述的发光二极管器件，其中，所述第一电极为阴极， 所述第二电极为阳极，所述载流子功能层为电子传输层，所述电子传输层的材料为氧化锌；
    或者，所述第一电极为阳极，所述第二电极为阴极，所述载流子功能层为空穴传输层，所述空穴传输层的材料为氧化镍。
  20. 一种显示面板，其中，包括如权利要求1-19任一项所述的发光二极管器件。
  21. 一种显示装置，其中，包括如权利要求20所述的显示面板。
  22. 一种发光二极管器件的制作方法，其中，包括：
    在载体基板上形成包括第一反应物的量子点膜层，所述第一反应物包括量子点本体，与所述量子点本体连接的配体分子A，以及与所述量子点本体连接的配体分子B；
    通过中转基板与所述量子点膜层接触，以使所述第一反应物中的所述配体分子B与所述中转基板形成氢键，粘起所述量子点膜层；
    将具有所述量子点膜层的所述中转基板与形成有修饰分子的衬底基板进行贴合，以使所述量子点膜层表面所述第一反应物的所述配体分子A，与所述修饰分子进行原子转移自由基聚合反应，并在所述量子点膜层内部进行持续原子转移自由基聚合反应，形成量子点发光层，其中，所述衬底基板形成有第一电极以及位于所述第一电极背离所述衬底基板一侧的载流子功能层，所述修饰分子连接于所述载流子功能层的背离所述第一电极的表面；
    移去所述中转基板；
    形成第二电极。
  23. 如权利要求22所述的制作方法，其中，所述在载体基板上形成包括第一反应物的量子点膜层，包括：
    在载体基板上形成具有初始配体的初始量子点膜层；
    在形成有所述初始量子点膜层的所述载体基板形成含有配体分子A和配体分子B的溶液，以使所述配体分子A、所述配体分子B与所述初始配体发生配体交换反应。
  24. 如权利要求23所述的制作方法，其中，所述在载体基板上形成具有初始配体的初始量子点膜层，包括：
    采用十八烷三甲氧基硅处理硅基基板；
    在所述硅基基板上形成具有油酸配体的初始量子点膜层。
  25. 如权利要求22所述的制作方法，其中，在将具有量子点膜层的所述中转基板与形成有修饰分子的载流子功能层的衬底基板进行贴合之前，所述制作方法还包括：
    提供一衬底基板；
    在所述衬底基板的一侧形成载流子功能层；
    在所述载流子功能层的表面形成含有所述修饰分子的溶液，以使所述修饰分子与所述载流子功能层表面的羟基偶联。
  26. 如权利要求25所述的制作方法，其中，在粘起所述量子点膜层之后，以及在将具有所述量子点膜层的所述中转基板与形成有修饰分子的衬底基板进行贴合之前，所述制作方法还包括：
    将粘接有所述量子点膜层的所述中转基板与具有沟槽的凹版接触，形成图案化的量子点膜层。
  27. 如权利要求22所述的制作方法，其中，在将具有所述量子点膜层的所述中转基板与形成有修饰分子的衬底基板进行贴合时，所述制作方法还包括：浸泡在氯化亚铜的苯甲醚溶液中。
  28. 如权利要求22所述的制作方法，其中，所述通过中转基板与所述量子点膜层接触，包括：
    通过材料为聚二甲基硅氧烷的基板与所述量子点膜层接触。
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