WO2020108070A1 - 一种量子点发光二极管的制备方法 - Google Patents

一种量子点发光二极管的制备方法 Download PDF

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WO2020108070A1
WO2020108070A1 PCT/CN2019/108335 CN2019108335W WO2020108070A1 WO 2020108070 A1 WO2020108070 A1 WO 2020108070A1 CN 2019108335 W CN2019108335 W CN 2019108335W WO 2020108070 A1 WO2020108070 A1 WO 2020108070A1
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quantum dot
dot light
layer
emitting diode
ligand compound
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PCT/CN2019/108335
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French (fr)
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聂志文
杨一行
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Tcl科技集团股份有限公司
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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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
    • H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H10K71/441—Thermal treatment, e.g. annealing in the presence of a solvent vapour in the presence of solvent vapors, e.g. solvent vapour annealing

Definitions

  • the present disclosure relates to the field of quantum dot light-emitting devices, and in particular to a method for preparing quantum dot light-emitting diodes.
  • a quantum dot is a semiconductor nanocrystal composed of a certain number of atoms, usually 1-10 nm in size and generally spherical. Its elemental composition is generally group II-VI or group III-V elements. The size of quantum dots is smaller than or close to the exciton Bohr radius of their corresponding bulk materials, and has obvious quantum dot confinement effect, thus exhibiting excellent optical performance.
  • Quantum dot light-emitting diode is a new display technology developed on the basis of the device structure of organic light-emitting diode.
  • the similarity between the two is that the principle of light emission is similar, that is, under the excitation of current, electron/hole pairs are injected into the light-emitting layer through the electron/hole transport layer, and electrons and holes recombine in the light-emitting layer to generate photons. Photons release energy in the form of light energy, thereby emitting light.
  • the difference between the two is that the light-emitting layer uses different materials.
  • the light-emitting layer of the organic light-emitting diode uses phosphorescent materials, while the light-emitting layer of the quantum dot light-emitting diode uses quantum dot materials.
  • quantum dot light emitting diodes have the advantages of low cost, narrow peak width, wide color gamut, and high color saturation, and can be prepared by printing, which is more suitable for the production of large-size displays.
  • quantum dot light-emitting diode devices In recent years, the performance of quantum dot light-emitting diode devices has achieved very rapid development, especially the efficiency and life indicators of red and green devices have tended to be commercialized. For the improvement of device performance, the optimization of quantum dot surface ligands plays an important role.
  • the quantum dots used in the preparation process of quantum dot light-emitting diode devices usually use long-chain ligands during the synthesis process. These long-chain ligands have an important role in stabilizing the synthesis of quantum dots, but they will Some adverse effects.
  • the long-chain ligands on the surface of quantum dots are inherently insulative, which can hinder the transport performance of carriers.
  • the long-chain ligands on the surface of quantum dots will increase the distance between quantum dots and affect the valence electricity transmission between quantum dots. Therefore, the ligands on the surface of quantum dots play a very important role in the development of high-performance quantum dot light-emitting diode devices.
  • the first way is to dissolve the quantum dots in a suitable organic solvent, and then add the required ligands for exchange. This kind of exchange method not only has a long time and low efficiency, but also the quantum dots after exchange are extremely unstable, and it is easy to aggregate and precipitate.
  • the second method is: after the quantum dots are prepared into a film in a quantum dot light-emitting diode device, the film can be immersed in a new ligand solution.
  • the biggest disadvantage of this method is that it will have some adverse effects on other membrane layers when the ligand is exchanged.
  • the purpose of the present disclosure is to provide a method for preparing quantum dot light-emitting diodes, aiming to solve the problem that the quantum dots after the existing ligands are prone to aggregation, precipitation, or other membrane layers during ligand exchange Issues that have an adverse impact.
  • the quantum dot light-emitting diode is a positive-type device, which includes the steps of:
  • a quantum dot light-emitting layer is formed on the surface of the short-chain ligand compound.
  • a preparation method of quantum dot light-emitting diode, the quantum dot light-emitting diode is an inversion device, which includes the steps of:
  • a quantum dot light-emitting layer is formed on the surface of the short-chain ligand compound.
  • the single-sided ligand of the quantum dot light-emitting layer can be completed exchange.
  • This method is conducive to the recombination of electrons and holes in the quantum dot light-emitting layer, reducing the occurrence of non-radiative transitions, thereby greatly improving the luminous efficiency.
  • the ligand exchange method of the present disclosure has the advantages of simple steps, short operation time, and can effectively avoid the influence on other membrane layers.
  • FIG. 1 is a schematic structural diagram of a positive-type quantum dot light-emitting diode provided in an embodiment of the present disclosure.
  • FIG. 2 is a schematic flowchart of a method for manufacturing a positive-type quantum dot light-emitting diode provided in an embodiment of the present disclosure.
  • FIG. 3 is a schematic structural diagram of a quantum dot light-emitting diode with an inverted structure provided in an embodiment of the present disclosure.
  • FIG. 4 is a schematic flow chart of a method for manufacturing a reverse-type quantum dot light-emitting diode provided in an embodiment of the present disclosure.
  • the present disclosure provides a method for manufacturing a quantum dot light emitting diode.
  • a quantum dot light emitting diode In order to make the purposes, technical solutions, and effects of the present disclosure clearer and more specific, the present disclosure will be described in further detail below. It should be understood that the specific embodiments described herein are only used to explain the present disclosure and are not intended to limit the present disclosure.
  • the structure of the quantum dot light-emitting diode is divided into two types: a positive-type device and a reverse-type device, and the quantum dot light-emitting diode of each structure may have multiple forms.
  • the quantum dot light-emitting diode shown in FIG. 1 will mainly introduce the quantum dot light-emitting diode shown in FIG. 1 as an example.
  • the hole functional layer in this embodiment is a hole injection layer and a hole transport layer on the hole injection layer, and the quantum dot light-emitting diode sequentially includes: a substrate, an anode, and a hole injection layer from bottom to top , A hole transport layer, a quantum dot light emitting layer, an electron transport layer, and a cathode, wherein the quantum dot light emitting layer is combined with a layer of short-chain ligand compound on the side near the anode, as shown in FIG. 2, the quantum dot emits light
  • the preparation method of the diode specifically includes steps:
  • a cathode is formed on the surface of the electron transport layer to obtain the quantum dot light-emitting diode.
  • the hole transport layer injects holes into the quantum dot light-emitting layer and the electron transport layer injects electrons into the quantum dot light-emitting layer. difference.
  • the injection rate of electrons is generally greater than the injection rate of holes. Therefore, it will cause a large number of electrons to accumulate in the quantum dot light-emitting layer. Excessive electrons will cause non-radiative transitions of excitons, thereby greatly reducing the recombination efficiency of holes and electrons.
  • the unilateral ligand exchange of the quantum dot light-emitting layer can be completed.
  • the quantum dot light-emitting layer grafted with the target ligand can accelerate the hole injection rate to a certain extent. This method is conducive to the recombination of electrons and holes in the quantum dot light-emitting layer, reducing the occurrence of non-radiative transitions, thereby greatly improving the luminous efficiency.
  • an efficient and fast quantum dot surface ligand exchange process is proposed. This method has the advantages of simple steps, short operation time, and can effectively avoid the impact on other membrane layers. .
  • a layer of short-chain ligand compound is deposited on the surface of the hole transport layer by vacuum evaporation.
  • the embodiments of the present disclosure are not limited to depositing a layer of short-chain ligand compound on the surface of the hole transport layer by vacuum evaporation, and may also deposit the layer on the surface of the hole transport layer by a solution method.
  • Short-chain ligand compounds Specifically, after dissolving the short-chain ligand compound in a non-polar solvent, the solution is annealed after being deposited on the surface of the hole transport layer using a solution method (such as inkjet printing, doctor coating, etc.), The short-chain ligand compound layer is formed.
  • the non-polar solvents include: toluene, n-octane, n-hexane, cyclohexane, isooctane, heptane, n-pentane, isopentane, chloroform, dichlorotoluene, toluene, chlorobenzene, tetrachloro One or more of toluene, ether, ethyl acetate, and isopropyl myristate.
  • the annealing temperature is: the temperature is 100-300° C., and the time is 15-120 mins.
  • the method further includes: using a vacuum evaporation method on the quantum A layer of long-chain ligand compound is deposited on the surface of the point light-emitting layer.
  • the exchanged quantum dot light emitting layer can also slow down the electron injection rate to a certain extent.
  • This method can further facilitate the recombination of electrons and holes in the quantum dot light-emitting layer, reduce the occurrence of non-radiative transitions, and thus greatly improve the luminous efficiency.
  • this method also has the advantages of simple steps, short operation time, and can effectively avoid the impact on other membrane layers.
  • the vacuum evaporation method is used to deposit a layer of short-chain ligand compound on the surface of the hole transport layer: the evaporation temperature is 50-200°C, and the evaporation time is 1- 60min.
  • the vacuum evaporation method is used to deposit a layer of long-chain ligand compound on the surface of the quantum dot light-emitting layer: the evaporation temperature is 50-200° C., and the evaporation time is 1- 60min.
  • the method further includes the steps of: removing the remaining ligand on the surface of the quantum dot light-emitting layer through a non-polar solvent, and performing annealing treatment.
  • the non-polar solvent is selected from one or more of chloroform, chlorobenzene, diethyl ether, ethyl acetate, and isopropyl myristate.
  • the conditions of the annealing process the temperature is 100-300° C., and the time is 15-120 min.
  • the short-chain ligand compound is selected from the group consisting of thiols with less than 8 carbon atoms in the main chain, thiophenols, sulfur-containing salts, organic amines with 2 to 10 carbon atoms, halides, etc. One or more.
  • the thiol having less than 8 carbon atoms in the main chain is selected from 3-mercaptopropionic acid, mercaptoethanol, mercaptohexanol, propanedithiol, 2-mercapto-3butanol, 1,2 -Ethane dithiol, 1,6-hexane dithiol, 1,4-dimercapto-2,3-butanediol, 6-mercaptohexanol, cysteine, propane-1,2,3- One or more of trithiol and 2,3-dimercapto-1-propanethiol.
  • the thiophenol is selected from one or more of benzenethiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, etc. .
  • the sulfur-containing salt includes one or more of ammonium thiocyanate, ammonium sulfide, dithiocarbamate, zinc dithiocarbamate, and the like.
  • the organic amine having 2 to 10 carbon atoms is selected from one or more of n-octylamine, decylamine, 1,2-ethylenediamine, diethylaminoethanol, and the like.
  • the halide is selected from hydrohalic acid, ammonium halide, and metal halide salt.
  • the metal halide salt is selected from one of Group IA, Group IIA and Group IIIA metals.
  • the halide includes: HF, NH 4 F, HCl, NH 4 Cl, HBr, NH 4 Br, LiF, KF, NaF, BeF 2 , MgF 2 , CaF 2 , AlF 3 , InF 3 , LiCl, NaCl, MgCl 2, CaCl 2, ZnCl 2, AlCl 3, GaCl 3, InCl 3, LiBr, NaBr, MgBr 2, CaBr 2, ZnBr 2, AlBr 3, GaBr 3, InBr 3, LiI, NaI, MgI 2, CaI 2.
  • the long-chain ligand compound is selected from one or both of a thiol having 8 or more carbon atoms in the main chain and an amino group-containing polymer.
  • the thiol having 8 or more carbon atoms in the main chain is selected from octyl mercaptan, dodecyl mercaptan, t-dodecyl mercaptan, 1,8-octanedithiol 11 -Mercaptoundecyl alcohol, 11-mercaptoundecanoic acid, 1,8-dimercapto-3,6-dithiooctane, 6,8-dimercaptooctanoic acid, zinc dodecyl mercaptan polymer and tri One or more of polythiocyanic acid and the like.
  • the amino group-containing polymer is selected from one or more of poly(amidoamine) dendrimer, polyetheramine (molecular weight greater than 230), amino silicone, and the like.
  • this embodiment will mainly introduce the manufacturing method of the quantum dot light-emitting diode shown in FIG. 3 as an example.
  • the electronic functional layer of this embodiment is an electron transport layer
  • the quantum dot light-emitting diode includes a substrate, a cathode, an electron transport layer, a quantum dot light emitting layer, a hole transport layer, a hole injection layer, and an anode in this order from bottom to top ,
  • the quantum dot light-emitting layer is combined with a layer of short-chain ligand compound on the side near the cathode, as shown in FIG. 4, the preparation method of the quantum dot light-emitting diode specifically includes steps:
  • An anode is formed on the surface of the hole injection layer to obtain the quantum dot light emitting diode.
  • the hole transport layer injects holes into the quantum dot light-emitting layer and the electron transport layer injects electrons into the quantum dot light-emitting layer. difference.
  • the injection rate of holes is generally greater than the injection rate of electrons. Therefore, a large amount of holes will be accumulated in the quantum dot light-emitting layer, and excessive holes will cause non-radiative transitions of excitons, thereby greatly reducing the recombination efficiency of holes and electrons.
  • the single quantum dot light-emitting layer can be completed Side ligand exchange.
  • the quantum dot light-emitting layer grafted with the target ligand can accelerate the injection rate of electrons to a certain extent.
  • This method is conducive to the recombination of electrons and holes in the quantum dot light-emitting layer, reducing the occurrence of non-radiative transitions, thereby greatly improving the luminous efficiency.
  • an efficient and fast quantum dot surface ligand exchange process is proposed. This method has the advantages of simple steps, short operation time, and can effectively avoid the impact on other membrane layers. .
  • a layer of short-chain ligand compound is deposited on the surface of the electron transport layer by vacuum evaporation.
  • the embodiments of the present disclosure are not limited to depositing a layer of short-chain ligand compound on the surface of the electron transport layer by vacuum evaporation, and may also deposit the short chain on the surface of the electron transport layer by using a solution method Ligand compounds. Specifically, after dissolving the short-chain ligand compound in a non-polar solvent, the solution is annealed after deposition on the surface of the electron transport layer by a solution method (such as inkjet printing, doctor coating, etc.) The short-chain ligand compound layer.
  • a solution method such as inkjet printing, doctor coating, etc.
  • the non-polar solvents include: toluene, n-octane, n-hexane, cyclohexane, isooctane, heptane, n-pentane, isopentane, chloroform, dichlorotoluene, toluene, chlorobenzene, tetrachloro One or more of toluene, ether, ethyl acetate, and isopropyl myristate.
  • the annealing temperature is: the temperature is 100-300° C., and the time is 15-120 mins.
  • the method further includes: A layer of long-chain ligand compound is deposited on the surface of the quantum dot luminescent layer.
  • the exchanged single-sided quantum dot light-emitting layer can slow down the hole injection rate to a certain extent.
  • This method can further facilitate the recombination of electrons and holes in the quantum dot light-emitting layer, reduce the occurrence of non-radiative transitions, and thus greatly improve the luminous efficiency.
  • this method also has the advantages of simple steps, short operation time, and can effectively avoid the impact on other membrane layers.
  • the vacuum evaporation method is used to deposit a layer of short-chain ligand compound on the surface of the electron transport layer: the evaporation temperature is 50-200° C., and the evaporation time is 1-60 min. .
  • the vacuum evaporation method is used to deposit a layer of long-chain ligand compound on the surface of the quantum dot light-emitting layer: the evaporation temperature is 50-200° C., and the evaporation time is 1- 60min.
  • the method further includes the steps of: removing the remaining ligand on the surface of the quantum dot light-emitting layer through a non-polar solvent, and performing annealing treatment.
  • the non-polar solvent is selected from one or more of chloroform, chlorobenzene, diethyl ether, ethyl acetate, and isopropyl myristate.
  • the conditions of the annealing process the temperature is 100-300° C., and the time is 15-120 min.
  • the short-chain ligand compound is selected from the group consisting of thiols with less than 8 carbon atoms in the main chain, thiophenols, sulfur-containing salts, organic amines with 2 to 10 carbon atoms, halides, etc. One or more.
  • the thiol having less than 8 carbon atoms in the main chain is selected from 3-mercaptopropionic acid, mercaptoethanol, mercaptohexanol, propanedithiol, 2-mercapto-3butanol, 1,2 -Ethane dithiol, 1,6-hexane dithiol, 1,4-dimercapto-2,3-butanediol, 6-mercaptohexanol, cysteine, propane-1,2,3- One or more of trithiol and 2,3-dimercapto-1-propanethiol.
  • the thiophenol is selected from one or more of benzenethiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, etc. .
  • the sulfur-containing salt includes one or more of ammonium thiocyanate, ammonium sulfide, dithiocarbamate, zinc dithiocarbamate, and the like.
  • the organic amine having 2 to 10 carbon atoms is selected from one or more of n-octylamine, decylamine, 1,2-ethylenediamine, diethylaminoethanol, and the like.
  • the halide is selected from hydrohalic acid, ammonium halide, and metal halide salt.
  • the metal halide salt is selected from one of Group IA, Group IIA and Group IIIA metals.
  • the halide includes: HF, NH 4 F, HCl, NH 4 Cl, HBr, NH 4 Br, LiF, KF, NaF, BeF 2 , MgF 2 , CaF 2 , AlF 3 , InF 3 , LiCl, NaCl, MgCl 2, CaCl 2, ZnCl 2, AlCl 3, GaCl 3, InCl 3, LiBr, NaBr, MgBr 2, CaBr 2, ZnBr 2, AlBr 3, GaBr 3, InBr 3, LiI, NaI, MgI 2, CaI 2.
  • the long-chain ligand compound is selected from one or both of a thiol having 8 or more carbon atoms in the main chain and an amino group-containing polymer.
  • the thiol having 8 or more carbon atoms in the main chain is selected from octyl mercaptan, dodecyl mercaptan, t-dodecyl mercaptan, 1,8-octanedithiol 11 -Mercaptoundecyl alcohol, 11-mercaptoundecanoic acid, 1,8-dimercapto-3,6-dithiooctane, 6,8-dimercaptooctanoic acid, zinc dodecyl mercaptan polymer and tri One or more of polythiocyanic acid and the like.
  • the amino group-containing polymer is selected from one or more of poly(amidoamine) dendrimer, polyetheramine (molecular weight greater than 230), amino silicone, and the like.
  • the obtained quantum dot light emitting diode can be packaged.
  • the packaging process may use commonly used machine packaging or manual packaging.
  • the oxygen content and the water content are both less than 0.1 ppm to ensure the stability of the device.
  • the preparation method of each layer may be a chemical method or a physical method, wherein the chemical method includes but is not limited to chemical vapor deposition method, continuous ion layer adsorption and reaction method, anodizing method, electrolytic deposition method, co-precipitation method.
  • One or more; physical methods include but are not limited to solution methods (such as spin coating method, printing method, knife coating method, dipping and pulling method, dipping method, spraying method, roll coating method, casting method, slot coating) Method or strip coating method, etc.), evaporation method (such as thermal evaporation method, electron beam evaporation method, magnetron sputtering method or multi-arc ion coating method, etc.), deposition method (such as physical vapor deposition method, atomic One or more of layer deposition method, pulsed laser deposition method, etc.).
  • the substrate may be a rigid material substrate, such as glass, or a flexible material substrate, such as PET or PI.
  • the material of the anode may be selected from Ag, Mo, Al, Cu, Au or their alloys; the material of the cathode may be selected from indium-doped tin oxide One or more of (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), and the like.
  • ITO indium-doped tin oxide
  • FTO fluorine-doped tin oxide
  • ATO antimony-doped tin oxide
  • AZO aluminum-doped zinc oxide
  • the material of the cathode may be selected from indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO) and One or more of aluminum-doped zinc oxide (AZO) and the like; the material of the anode may be selected from Ag, Mo, Al, Cu, Au, or alloys thereof.
  • the thickness of the cathode is 90-110 nm; the thickness of the anode is 30-110 nm.
  • the material of the electron transport layer may be selected from materials with good electron transport performance, such as but not limited to ZnO, ZrO, TiO 2 , Alq3, TAZ, TPBI, PBD, BCP, Bphen, etc. One or more.
  • the thickness of the electron transport layer is 10-100 nm.
  • the material of the quantum dot light-emitting layer may be selected from group II-VI compounds, group II-V compounds, group IV-VI compounds, group I-III-VI compounds, and group I-II-IV-VI One or more of compounds and the like.
  • the thickness of the quantum dot light emitting layer is 30-100 nm.
  • the material of the hole transport layer may be a small molecular organic substance or a high molecular conductive polymer, for example, it may be selected from TFB, PVK, Poly-TBP, Poly-TPD, NPB, TCTA, TAPC , CBP, PEODT: one or more of PSS, MoO 3 , WoO 3 , NiO, CuO, V 2 O 5 and CuS.
  • the thickness of the hole transport layer is 30-100 nm.
  • the material of the hole injection layer may be selected from one or more of PEODT: PSS, MoO 3 , WoO 3 , NiO, HATCN, CuO, V 2 O 5 and CuS.
  • the thickness of the hole injection layer is 30-100 nm.
  • the bottom electrode, the hole injection layer and the hole transport layer are sequentially prepared on the substrate;
  • a layer of 1,6-hexanedithiol was evaporated on the hole transport layer by vacuum evaporation method, in which the evaporation temperature was 80°C and the time was 2min; the quantum dot light-emitting layer was prepared on the hole transport layer for ligand Exchange, after the vapor deposition is completed, the surface of the film is washed with ether, and then placed at 100 °C for 20min;
  • An electron transport layer and a top electrode are sequentially prepared on the quantum dot light-emitting layer.
  • the substrate is a glass substrate; the bottom electrode is ITO with a thickness of 100 nm; the hole injection layer is PEDOT:PSS with a thickness of 40 nm; the hole transport layer is TFB with a thickness of 80 nm; the quantum dot light-emitting layer is InP/ ZnS with a thickness of 100 nm; the electron transport layer is ZnO with a thickness of 60 nm; the top electrode is Al with a thickness of 50 nm.
  • the bottom electrode, the hole injection layer and the hole transport layer are sequentially prepared on the substrate;
  • a layer of 1,2-benzenedithiol was vapor-deposited on the hole transport layer by vacuum evaporation method, in which the evaporation temperature was 80°C and the time was 2min; the quantum dot light-emitting layer was prepared on the hole transport layer for ligand Exchange, and then clean the surface of the membrane with ether, and then anneal at 100 °C for 20min;
  • An electron transport layer and a top electrode are sequentially prepared on the quantum dot light-emitting layer.
  • the substrate is a glass substrate; the bottom electrode is ITO with a thickness of 100 nm; the hole injection layer is PEDOT:PSS with a thickness of 40 nm; the hole transport layer is TFB with a thickness of 80 nm; the quantum dot light-emitting layer is InP/ ZnS with a thickness of 100 nm; the electron transport layer is ZnO with a thickness of 60 nm; the top electrode is Al with a thickness of 50 nm.
  • the bottom electrode, the hole injection layer and the hole transport layer are sequentially prepared on the substrate;
  • a layer of 1,2-ethanedithiol was evaporated on the hole transport layer by vacuum evaporation method, in which the evaporation temperature was 80°C and the time was 2min; the quantum dot light-emitting layer was prepared on the hole transport layer for preparation Body exchange, then the membrane surface was washed with ether, and then placed at 100 °C annealing 20min;
  • An electron transport layer and a top electrode are sequentially prepared on the quantum dot light-emitting layer.
  • the substrate is a glass substrate; the bottom electrode is ITO with a thickness of 100 nm; the hole injection layer is PEDOT:PSS with a thickness of 40 nm; the hole transport layer is TFB with a thickness of 80 nm; the quantum dot light-emitting layer is InP/ ZnS with a thickness of 100 nm; the electron transport layer is ZnO with a thickness of 60 nm; the top electrode is Al with a thickness of 50 nm.
  • a layer of 1,6-hexanedithiol was evaporated on the electron transport layer by vacuum evaporation method, where the evaporation temperature was 80°C and the time was 2 minutes; a quantum dot luminescent layer was prepared on the electron transport layer for ligand exchange, Then, the surface of the membrane was cleaned with ether, and then placed at 100°C for 20 minutes for annealing;
  • a hole transport layer, a hole injection layer, and a top electrode are sequentially prepared on the quantum dot light-emitting layer.
  • the substrate is a glass substrate;
  • the bottom electrode is Al with a thickness of 50 nm;
  • the electron transport layer is ZnO with a thickness of 60 nm;
  • the quantum dot light emitting layer is InP/ZnS with a thickness of 100 nm;
  • the hole transport layer is TFB , Thickness 80nm; hole injection layer PEDOT: PSS, thickness 40nm; top electrode ITO, thickness 100nm.
  • a layer of 1,2-benzenedithiol is deposited on the electron transport layer by vacuum evaporation, where the evaporation temperature is 80°C and the time is 2 minutes; a quantum dot light-emitting layer is prepared on the electron transport layer for ligand exchange, Then, the surface of the membrane was cleaned with ether, and then placed at 100°C for 20 minutes for annealing;
  • a hole transport layer, a hole injection layer, and a top electrode are sequentially prepared on the quantum dot light-emitting layer.
  • the substrate is a glass substrate; the bottom electrode is Al with a thickness of 50 nm; the electron transport layer is ZnO with a thickness of 60 nm; the quantum dot light emitting layer is InP/ZnS with a thickness of 100 nm; the hole transport layer is TFB with a thickness 80nm; the hole injection layer is PEDOT:PSS with a thickness of 40nm; the top electrode is ITO with a thickness of 100nm.
  • a layer of 1,2-ethanedithiol was evaporated on the electron transport layer by vacuum evaporation method, in which the evaporation temperature was 80°C and the time was 2min; the quantum dot light-emitting layer was prepared on the electron transport layer for ligand exchange Then, the surface of the membrane is washed with ether, and then placed at 100 °C for 20min;
  • a hole transport layer, a hole injection layer, and a top electrode are sequentially prepared on the quantum dot light-emitting layer.
  • the substrate is a glass substrate;
  • the bottom electrode is Al with a thickness of 50 nm;
  • the electron transport layer is ZnO with a thickness of 60 nm;
  • the quantum dot light emitting layer is InP/ZnS with a thickness of 100 nm;
  • the hole transport layer is TFB , Thickness 80nm; hole injection layer PEDOT: PSS, thickness 40nm; top electrode ITO, thickness 100nm.
  • the present disclosure provides a quantum dot light emitting diode and a preparation method thereof.
  • the present disclosure by preparing a layer of short-chain ligand compound on the surface of the substrate during the preparation of the quantum dot light emitting diode, and then preparing the quantum dot light emitting layer, the unilateral ligand exchange of the quantum dot light emitting layer can be completed.
  • This method is conducive to the recombination of electrons and holes in the quantum dot light-emitting layer, reducing the occurrence of non-radiative transitions, thereby greatly improving the luminous efficiency.
  • the ligand exchange method of the present disclosure has the advantages of simple steps, short operation time, and can effectively avoid the influence on other membrane layers. Further, the present disclosure can continue to vapor-deposit a layer of long-chain ligand compound on the surface of the quantum dot light-emitting layer to complete the ligand exchange on the other side of the quantum dot light-emitting layer. This method can further facilitate the recombination of electrons and holes in the quantum dot light-emitting layer, reduce the occurrence of non-radiative transitions, and thus greatly improve the luminous efficiency. At the same time, this method also has the advantages of simple steps, short operation time, and can effectively avoid the impact on other membrane layers.

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  • Electroluminescent Light Sources (AREA)

Abstract

一种量子点发光二极管的制备方法，所述量子点发光二极管为正型器件，方法包括步骤：提供阳极；在所述阳极表面形成空穴功能层；在所述空穴功能层表面形成一层短链配体化合物；在所述短链配体化合物表面形成量子点发光层。该方法不但可以获得稳定的量子点，且可以大大提高电子/空穴对在激子中的复合，提高器件效率。同时，该配体交换方法具有步骤简单、操作时间短、且能有效的避免对其他膜层的影响等优点。

Description

一种量子点发光二极管的制备方法 技术领域
本公开涉及量子点发光器件领域，尤其涉及一种量子点发光二极管的制备方法。
背景技术
量子点是一种由一定数量的原子组成的尺寸通常在1～10nm、一般为球形的半导体纳米晶体，其元素组成一般为II-VI族或III-V族元素。量子点的尺寸小于或接近其相应体相材料的激子波尔半径，具有明显的量子点限域效应，从而表现为优异的光学性能。
量子点发光二极管是一种借鉴有机发光二极管的器件结构之上发展起来的一种新型显示技术。两者间的相似之处在于其发光原理相近，即：在电流的激发下，电子/空穴对通过电子/空穴传输层注入发光层，电子和空穴在发光层中发生复合产生光子，光子以光能的形式释放能量，从而发光。两者间的差别在于发光层所使用的材料不同，有机发光二极管的发光层使用的是磷光材料，而量子点发光二极管的发光层所使用的是量子点材料。与有机发光二极管相比，量子点发光二极管具有成本低、峰宽窄、色域宽，色彩饱和度高等优点，且可采用印刷的方式来制备，更加适合大尺寸显示器的生产。
近年来，量子点发光二极管器件性能取得了非常快速的发展，尤其是红绿器件的效率和寿命指标已趋于商业化应用。对于器件性能的提升，量子点表面配体的优化起了很重要的作用。目前，量子点发光二极管器件制备过程中所使用的量子点在合成的过程中通常会使用长链配体，这些长链的配体对稳定量子点的合成具有重要作用，但是在器件制备方面会产生一些不利影响。在量子点发光二极管器件中，量子点表面的长链配体由于自身具有绝缘性，会阻碍载流子的传输性能。同时，量子点表面长链配体会增加量子点间的距离，影响了量子点间的价电传输。因此，量子点表面的配体对高性能的量子点发光二极管器件的开发具有非常重要的作用。目前，实现量子点表面配体交换的方式主要有两种。第一种方式是：将量子点溶解在合适的有机溶剂中，然后加入所需的配体进行交换即可。该种交换方法不仅时间长、效率低、且交换后的量子点极不稳定，容易发 生聚集、沉淀。第二种方式是：将量子点在量子点发光二极管器件中制备成膜后，将薄膜浸入到新的配体溶液中即可。该种方法最大的弊端在于在进行配体交换的同时会对其他膜层产生一些不利的影响。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本公开的目的在于提供一种量子点发光二极管的制备方法，旨在解决现有配体后的量子点容易产生聚集、沉淀，或者配体交换时对其他膜层产生不利影响的问题。
本公开的技术方案如下：
一种量子点发光二极管的制备方法，所述量子点发光二极管为正型器件，其中，包括步骤：
提供阳极；
在所述阳极表面形成空穴功能层；
在所述空穴功能层表面形成一层短链配体化合物；
在所述短链配体化合物表面形成量子点发光层。
一种量子点发光二极管的制备方法，所述量子点发光二极管为反型器件，其中，包括步骤：
提供阴极；
在所述阴极表面形成电子功能层；
在所述电子功能层表面形成一层短链配体化合物；
在所述短链配体化合物表面形成量子点发光层。
有益效果：本公开通过在制备量子点发光二极管过程中，先在空穴功能层表面形成一层短链配体化合物，然后制备量子点发光层，即可完成量子点发光层的单侧配体交换。该方式有利于电子和空穴在量子点发光层进行复合，减少非辐射跃迁的发生，从而大大提高发光效率。同时，与现有配体交换方法相比，本公开配体交换方法具有步骤简单、 操作时间短、且能有效的避免对其他膜层的影响等优点。
附图说明
图1为本公开实施例中提供的一种正型结构的量子点发光二极管的结构示意图。
图2为本公开实施例中提供的一种正型结构的量子点发光二极管的制备方法的流程示意图。
图3为本公开实施例中提供的一种反型结构的量子点发光二极管的结构示意图。
图4为本公开实施例中提供的一种反型结构的量子点发光二极管的制备方法的流程示意图。
具体实施方式
本公开提供一种量子点发光二极管的制备方法，为使本公开的目的、技术方案及效果更加清楚、明确，以下对本公开进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本公开，并不用于限定本公开。
本实施例中，量子点发光二极管的结构分为两种：正型器件和反型器件，每种结构的量子点发光二极管可以有多种形式。
对于正型结构的量子点发光二极管，本实施例将主要以如图1所示的量子点发光二极管为例进行介绍。本实施例的空穴功能层为空穴注入层和位于所述空穴注入层上的空穴传输层，所述量子点发光二极管自下而上依次包括：衬底、阳极、空穴注入层、空穴传输层、量子点发光层、电子传输层和阴极，其中所述量子点发光层靠近所述阳极一侧结合有一层短链配体化合物，如图2所示，所述量子点发光二极管的制备方法具体包括步骤：
提供衬底，在所述衬底表面形成阳极；
在所述阳极表面形成空穴注入层；
在所述空穴注入层表面形成空穴传输层；
在所述空穴传输层表面形成一层短链配体化合物；
在所述短链配体化合物表面形成量子点发光层；
在所述量子点发光层表面形成电子传输层；
在所述电子传输层表面形成阴极，得到所述量子点发光二极管。
与传统的量子点发光二极管制备相比，器件效率低的主要原因在于空穴传输层将空穴注入到量子点发光层的速率和电子传输层将电子注入到量子点发光层的速率存在较大差异。一般而言，对于正式结构的量子点发光二极管，电子的注入速率普遍大于空穴的注入速率。因此，会造成电子在量子点发光层中大量堆积，过量的电子会引发激子的非辐射跃迁，从而大大降低空穴和电子的复合效率。通过在制备该量子点发光二极管的过程中，先在空穴传输层上形成一层短链配体化合物，然后制备量子点发光层，即可完成量子点发光层的单侧配体交换，交换后的接枝有目标配体的量子点发光层可以一定程度上加快空穴的注入速率。这种方式有利于电子和空穴在量子点发光层进行复合，减少非辐射跃迁的发生，从而大大提高发光效率。同时，针对传统配体交换工艺存在的问题，提出一种高效、快速的量子点表面配体交换工艺，该方法具有步骤简单、操作时间短、且能有效的避免对其他膜层的影响等优点。
在一些实施方式中，采用真空蒸镀的方法在所述空穴传输层表面沉积一层短链配体化合物。
需说明的是，本公开实施例不限于采用真空蒸镀的方法在所述空穴传输层表面沉积一层短链配体化合物，也可以采用溶液法在所述空穴传输层表面沉积所述短链配体化合物。具体的，可以将所述短链配体化合物溶于非极性溶剂后，将所述溶液采用溶液法(例如喷墨打印、刮涂等方法)在所述空穴传输层表面沉积后退火，形成所述短链配体化合物层。
其中所述非极性溶剂包括：甲苯、正辛烷、正己烷、环己烷、异辛烷、庚烷、正戊烷、异戊烷、氯仿、二氯甲苯、甲苯、氯苯、四氯甲苯、乙醚、乙酸乙酯、肉豆蔻酸异丙酯中的一种或多种。
所述退火温度为：温度为100～300℃，时间为15～120mins。
在一些实施方式中，在所述短链配体化合物表面形成量子点发光层之后，在所述量 子点发光层表面形成电子传输层之前，还包括步骤：采用真空蒸镀的方法在所述量子点发光层表面沉积一层长链配体化合物。
本实施例中，考虑到接枝短链配体化合物的量子点发光层加快空穴的注入速率仍较有限的问题，通过继续在量子点发光层上蒸镀一层长链配体化合物，待完成量子点发光层该侧配体交换后，交换后的量子点发光层还可以一定程度上减慢电子的注入速率。这种方式可以进一步地利于电子和空穴在量子点发光层进行复合，减少非辐射跃迁的发生，从而大大提高发光效率。同时，该方法同样具有步骤简单、操作时间短、且能有效的避免对其他膜层的影响等优点。
在一些实施方式中，所述采用真空蒸镀的方法在所述空穴传输层表面沉积一层短链配体化合物的条件：蒸镀的温度为50-200℃，蒸镀的时间为1-60min。
在一些实施方式中，所述采用真空蒸镀的方法在所述量子点发光层表面沉积一层长链配体化合物的条件：蒸镀的温度为50-200℃，蒸镀的时间为1-60min。
在一些实施方式中，所述配体交换结束之后，还包括步骤：通过非极性溶剂将所述量子点发光层表面残余的配体清除，进行退火处理。在一些实施方式中，所述非极性溶剂选自氯仿、氯苯、乙醚、乙酸乙酯和肉豆蔻酸异丙酯中一种或多种。在一些实施方式中，所述退火处理的条件：温度为100-300℃，时间为15-120min。
在一些实施方式中，所述短链配体化合物选自主链碳原子数小于8的硫醇、硫酚、含硫的盐、碳原子数为2-10的有机胺和卤化物等中的一种或多种。
进一步在一些实施方式中，所述主链碳原子数小于8的硫醇选自3-巯基丙酸、巯基乙醇、巯基己醇、丙二硫醇、2-巯基-3丁醇、1，2-乙烷二硫醇、1,6-己二硫醇、1，4-二巯基-2，3-丁二醇、6-巯基己醇、半胱氨酸、丙烷-1,2,3-三硫醇和2，3-二巯基-1-丙硫醇等中的一种或多种。
进一步在一些实施方式中，所述硫酚选自苯硫醇、1，2-苯二硫醇、1，3-苯二硫醇和1，4-苯二硫醇等中的一种或多种。
进一步在一些实施方式中，所述含硫的盐包括硫氰酸铵、硫化铵、二硫代氨基甲酸酯和二硫代氨基甲酸锌等中的一种或多种。
进一步在一些实施方式中，所述碳原子数为2-10的有机胺选自正辛胺、癸胺、1，2-乙二胺和二乙氨基乙醇等中的一种或多种。
进一步在一些实施方式中，所述卤化物选自氢卤酸、卤化铵和金属卤化物盐。其中所述金属卤化物盐选自IA族、IIA族和IIIA族金属中的一种。作为举例，所述卤化物包括：HF、NH 4F、HCl、NH 4Cl、HBr、NH 4Br、LiF、KF、NaF、BeF 2、MgF 2、CaF 2、AlF 3、InF 3、LiCl、NaCl、MgCl 2、CaCl 2、ZnCl 2、AlCl 3、GaCl 3、InCl 3、LiBr、NaBr、MgBr 2、CaBr 2、ZnBr 2、AlBr 3、GaBr 3、InBr 3、LiI、NaI、MgI 2、CaI 2、ZnI 2、AlBr 3、GaI 3、InI 3、碘化四丁基铵、溴化四丁基铵、氯化四丁基铵和氟化四丁基铵等中的一种或多种。
在一些实施方式中，所述长链配体化合物选自主链碳原子数大于等于8的硫醇和含氨基的聚合物中的一种或两种。
进一步在一些实施方式中，所述主链碳原子数大于等于8的硫醇选自辛基硫醇、十二烷基硫醇、叔-十二硫醇、1,8-辛二硫醇11-巯基十一醇、11-巯基十一烷酸、1,8-二巯基-3,6-二硫杂辛烷、6，8-二巯基辛酸、十二烷基硫醇锌聚合物和三聚硫氰酸等中的一种或多种。
进一步在一些实施方式中，所述含氨基的聚合物选自聚(酰氨基胺)树枝状大分子、聚醚胺(分子量大于230)和氨基硅酮等中的一种或多种。
对于反型结构的量子点发光二极管的制备方法，本实施例将主要以如图3所示的量子点发光二极管的制备方法为例进行介绍。本实施例的电子功能层为电子传输层，所述量子点发光二极管自下而上依次包括：衬底、阴极、电子传输层、量子点发光层、空穴传输层、空穴注入层和阳极，其中所述量子点发光层靠近所述阴极一侧结合有一层短链配体化合物，如图4所示，所述量子点发光二极管的制备方法具体包括步骤：
提供衬底，在所述衬底表面形成阴极；
在所述阴极表面形成电子传输层；
在所述电子传输层表面形成一层短链配体化合物；
在所述短链配体化合物表面形成量子点发光层；
在所述量子点发光层表面形成空穴传输层；
在所述空穴传输层表面形成空穴注入层；
在所述空穴注入层表面形成阳极，得到所述量子点发光二极管。
与传统的量子点发光二极管制备相比，器件效率低的主要原因在于空穴传输层将空穴注入到量子点发光层的速率和电子传输层将电子注入到量子点发光层的速率存在较大差异。一般而言，对于反式结构的量子点发光二极管，空穴的注入速率普遍大于电子的注入速率。因此，会造成空穴在量子点发光层中大量堆积，过量的空穴会引发激子的非辐射跃迁，从而大大降低空穴和电子的复合效率。通过在制备该量子点发光二极管过程中，在电子传输层表面形成一层短链配体化合物，然后在所述短链配体化合物表面形成量子点发光层，即可完成量子点发光层的单侧配体交换，交换后的接枝有目标配体的量子点发光层可以一定程度上加快电子的注入速率。这种方式有利于电子和空穴在量子点发光层进行复合，减少非辐射跃迁的发生，从而大大提高发光效率。同时，针对传统配体交换工艺存在的问题，提出一种高效、快速的量子点表面配体交换工艺，该方法具有步骤简单、操作时间短、且能有效的避免对其他膜层的影响等优点。
在一些实施方式中，采用真空蒸镀的方法在所述电子传输层表面沉积一层短链配体化合物。
需说明的是，本公开实施例不限于采用真空蒸镀的方法在所述电子传输层表面沉积一层短链配体化合物，也可以采用溶液法在所述电子传输层表面沉积所述短链配体化合物。具体的，可以将所述短链配体化合物溶于非极性溶剂后，将所述溶液采用溶液法(例如喷墨打印、刮涂等方法)在所述电子传输层表面沉积后退火，形成所述短链配体化合物层。
其中所述非极性溶剂包括：甲苯、正辛烷、正己烷、环己烷、异辛烷、庚烷、正戊烷、异戊烷、氯仿、二氯甲苯、甲苯、氯苯、四氯甲苯、乙醚、乙酸乙酯、肉豆蔻酸异丙酯中的一种或多种。
所述退火温度为：温度为100～300℃，时间为15～120mins。
在一些实施方式中，在所述短链配体化合物表面形成量子点发光层之后，在所述量 子点发光层表面形成空穴传输层之前，还包括步骤：采用真空蒸镀的方法在所述量子点发光层表面沉积一层长链配体化合物。
本实施例中，考虑到接枝短链配体化合物的量子点发光层加快电子的注入速率仍较有限的问题，通过继续在量子点发光层表面蒸镀一层长链配体化合物，待完成量子点表面该侧配体交换后，交换后的单侧量子点发光层可以一定程度上减慢空穴的注入速率。这种方式可以进一步地利于电子和空穴在量子点发光层进行复合，减少非辐射跃迁的发生，从而大大提高发光效率。同时，该方法同样具有步骤简单、操作时间短、且能有效的避免对其他膜层的影响等优点。
在一些实施方式中，所述采用真空蒸镀的方法在所述电子传输层表面沉积一层短链配体化合物的条件：蒸镀的温度为50-200℃，蒸镀的时间为1-60min。
在一些实施方式中，所述采用真空蒸镀的方法在所述量子点发光层表面沉积一层长链配体化合物的条件：蒸镀的温度为50-200℃，蒸镀的时间为1-60min。
在一些实施方式中，所述配体交换结束之后，还包括步骤：通过非极性溶剂将所述量子点发光层表面残余的配体清除，进行退火处理。在一些实施方式中，所述非极性溶剂选自氯仿、氯苯、乙醚、乙酸乙酯和肉豆蔻酸异丙酯中一种或多种。在一些实施方式中，所述退火处理的条件：温度为100-300℃，时间为15-120min。
在一些实施方式中，所述短链配体化合物选自主链碳原子数小于8的硫醇、硫酚、含硫的盐、碳原子数为2-10的有机胺和卤化物等中的一种或多种。
进一步在一些实施方式中，所述主链碳原子数小于8的硫醇选自3-巯基丙酸、巯基乙醇、巯基己醇、丙二硫醇、2-巯基-3丁醇、1，2-乙烷二硫醇、1,6-己二硫醇、1，4-二巯基-2，3-丁二醇、6-巯基己醇、半胱氨酸、丙烷-1,2,3-三硫醇和2，3-二巯基-1-丙硫醇等中的一种或多种。
进一步在一些实施方式中，所述硫酚选自苯硫醇、1，2-苯二硫醇、1，3-苯二硫醇和1，4-苯二硫醇等中的一种或多种。
进一步在一些实施方式中，所述含硫的盐包括硫氰酸铵、硫化铵、二硫代氨基甲酸酯和二硫代氨基甲酸锌等中的一种或多种。
进一步在一些实施方式中，所述碳原子数为2-10的有机胺选自正辛胺、癸胺、1，2-乙二胺和二乙氨基乙醇等中的一种或多种。
进一步在一些实施方式中，所述卤化物选自氢卤酸、卤化铵和金属卤化物盐。其中所述金属卤化物盐选自IA族、IIA族和IIIA族金属中的一种。作为举例，所述卤化物包括：HF、NH 4F、HCl、NH 4Cl、HBr、NH 4Br、LiF、KF、NaF、BeF 2、MgF 2、CaF 2、AlF 3、InF 3、LiCl、NaCl、MgCl 2、CaCl 2、ZnCl 2、AlCl 3、GaCl 3、InCl 3、LiBr、NaBr、MgBr 2、CaBr 2、ZnBr 2、AlBr 3、GaBr 3、InBr 3、LiI、NaI、MgI 2、CaI 2、ZnI 2、AlBr 3、GaI 3、InI 3、碘化四丁基铵、溴化四丁基铵、氯化四丁基铵和氟化四丁基铵等中的一种或多种。
在一些实施方式中，所述长链配体化合物选自主链碳原子数大于等于8的硫醇和含氨基的聚合物中的一种或两种。
进一步在一些实施方式中，所述主链碳原子数大于等于8的硫醇选自辛基硫醇、十二烷基硫醇、叔-十二硫醇、1,8-辛二硫醇11-巯基十一醇、11-巯基十一烷酸、1,8-二巯基-3,6-二硫杂辛烷、6，8-二巯基辛酸、十二烷基硫醇锌聚合物和三聚硫氰酸等中的一种或多种。
进一步在一些实施方式中，所述含氨基的聚合物选自聚(酰氨基胺)树枝状大分子、聚醚胺(分子量大于230)和氨基硅酮等中的一种或多种。
本实施例中，可以对得到的量子点发光二极管进行封装处理。其中所述封装处理可采用常用的机器封装，也可以采用手动封装。在一些实施方式中，所述封装处理的环境中，氧含量和水含量均低于0.1ppm，以保证器件的稳定性。
本实施例中，各层制备方法可以是化学法或物理法，其中化学法包括但不限于化学气相沉积法、连续离子层吸附与反应法、阳极氧化法、电解沉积法、共沉淀法中的一种或多种；物理法包括但不限于溶液法(如旋涂法、印刷法、刮涂法、浸渍提拉法、浸泡法、喷涂法、滚涂法、浇铸法、狭缝式涂布法或条状涂布法等)、蒸镀法(如热蒸镀法、电子束蒸镀法、磁控溅射法或多弧离子镀膜法等)、沉积法(如物理气相沉积法、原子层沉积法、脉冲激光沉积法等)中的一种或多种。
本实施例中，所述衬底可以为刚性材质的衬底，如玻璃等，也可以为柔性材质的衬底，如PET或PI等中的一种。
本实施例中，对于正型结构的量子点发光二极管，所述阳极的材料可以选自Ag、Mo、Al、Cu、Au或它们的合金；所述阴极的材料可以选自铟掺杂氧化锡(ITO)、氟掺杂氧化锡(FTO)、锑掺杂氧化锡(ATO)和铝掺杂氧化锌(AZO)等中的一种或多种。所述阳极的厚度为30-110nm；所述阴极的厚度为90-110nm。
本实施例中，对于反型结构的量子点发光二极管，所述阴极的材料可以选自铟掺杂氧化锡(ITO)、氟掺杂氧化锡(FTO)、锑掺杂氧化锡(ATO)和铝掺杂氧化锌(AZO)等中的一种或多种；所述阳极的材料可以选自Ag、Mo、Al、Cu、Au或它们的合金。所述阴极的厚度为90-110nm；所述阳极的厚度为30-110nm。
本实施例中，所述电子传输层的材料可以选自具有良好电子传输性能的材料，例如可以为但不限于ZnO、ZrO、TiO 2、Alq3、TAZ、TPBI、PBD、BCP、Bphen等中的一种或多种。所述电子传输层的厚度为10-100nm。
本实施例中，所述量子点发光层的材料可以选自II-VI族化合物、II-V族化合物、IV-VI族化合物、I-III-VI族化合物和I-II-IV-VI族化合物等中的一种或多种。所述量子点发光层的厚度为30-100nm。
本实施例中，所述空穴传输层的材料可以是小分子有机物，也可以是高分子导电聚合物，例如可以选自TFB、PVK、Poly-TBP、Poly-TPD、、NPB、TCTA、TAPC、CBP、PEODT：PSS、MoO 3、WoO 3、NiO、CuO、V 2O 5和CuS等中的一种或多种。所述空穴传输层的厚度为30-100nm。
本实施例中，所述空穴注入层的材料可以选自PEODT：PSS、MoO 3、WoO 3、NiO、HATCN、CuO、V 2O 5和CuS等中的一种或多种。所述空穴注入层的厚度为30-100nm。
下面通过实施例对本公开进行详细说明。
实施例1
本实施例的量子点发光二极管的制备方法如下：
在衬底上依次制备底电极、空穴注入层和空穴传输层；
在空穴传输层上通过真空蒸镀法蒸镀一层1,6-己二硫醇，其中蒸镀温度为80℃，时间为2min；在空穴传输层上制备量子点发光层进行配体交换，待蒸镀完成后对膜的表面进行乙醚清洗，然后置于100℃下退火20min；
在量子点发光层上依次制备电子传输层和顶电极。
其中，所述衬底为玻璃基底；底电极为ITO，厚度为100nm；空穴注入层为PEDOT:PSS，厚度为40nm；空穴传输层为TFB，厚度为80nm；量子点发光层为InP/ZnS，厚度为100nm；所述电子传输层为ZnO，厚度为60nm；顶电极为Al，厚度为50nm。
实施例2
本实施例的量子点发光二极管的制备方法如下：
在衬底上依次制备底电极、空穴注入层和空穴传输层；
在空穴传输层上通过真空蒸镀法蒸镀一层1，2-苯二硫醇，其中蒸镀温度为80℃，时间为2min；在空穴传输层上制备量子点发光层进行配体交换，然后对膜的表面进行乙醚清洗，再置于100℃下退火20min；
在量子点发光层上依次制备电子传输层和顶电极。
其中，所述衬底为玻璃基底；底电极为ITO，厚度为100nm；空穴注入层为PEDOT:PSS，厚度为40nm；空穴传输层为TFB，厚度为80nm；量子点发光层为InP/ZnS，厚度为100nm；所述电子传输层为ZnO，厚度为60nm；顶电极为Al，厚度为50nm。
实施例3
本实施例的量子点发光二极管的制备方法如下：
在衬底上依次制备底电极、空穴注入层和空穴传输层；
在空穴传输层上通过真空蒸镀法蒸镀一层1，2-乙烷二硫醇，其中蒸镀温度为80℃，时间为2min；在空穴传输层上制备量子点发光层进行配体交换，然后对膜的表面进行乙醚清洗，再置于100℃下退火20min；
在量子点发光层上依次制备电子传输层和顶电极。
其中，所述衬底为玻璃基底；底电极为ITO，厚度为100nm；空穴注入层为PEDOT:PSS，厚度为40nm；空穴传输层为TFB，厚度为80nm；量子点发光层为InP/ZnS， 厚度为100nm；所述电子传输层为ZnO，厚度为60nm；顶电极为Al，厚度为50nm。
实施例4
本实施例的量子点发光二极管的制备方法如下：
在衬底上依次制备底电极和电子传输层；
在电子传输层上通过真空蒸镀法蒸镀一层1,6-己二硫醇，其中蒸镀温度为80℃，时间为2min；在电子传输层上制备量子点发光层进行配体交换，然后对膜的表面进行乙醚清洗，再置于100℃下退火20min；
在量子点发光层上依次制备空穴传输层、空穴注入层和顶电极。
其中，所述衬底为玻璃基底；底电极为Al，厚度为50nm；所述电子传输层为ZnO，厚度为60nm；量子点发光层为InP/ZnS，厚度为100nm；空穴传输层为TFB，厚度为80nm；空穴注入层为PEDOT:PSS，厚度为40nm；顶电极为ITO，厚度为100nm。
实施例5
本实施例的量子点发光二极管的制备方法如下：
在衬底上依次制备底电极和电子传输层；
在电子传输层上通过真空蒸镀法蒸镀一层1，2-苯二硫醇，其中蒸镀温度为80℃，时间为2min；在电子传输层上制备量子点发光层进行配体交换，然后对膜的表面进行乙醚清洗，再置于100℃下退火20min；
在量子点发光层上依次制备空穴传输层、空穴注入层和顶电极。
其中，所述衬底为玻璃基底；底电极为Al，厚度为50nm；电子传输层为ZnO，厚度为60nm；量子点发光层为InP/ZnS，厚度为100nm；空穴传输层为TFB，厚度为80nm；空穴注入层为PEDOT:PSS，厚度为40nm；顶电极为ITO，厚度为100nm。
实施例6
本实施例的量子点发光二极管的制备方法如下：
在衬底上依次制备底电极和电子传输层；
在电子传输层上通过真空蒸镀法蒸镀一层1，2-乙烷二硫醇，其中蒸镀温度为80℃，时间为2min；在电子传输层上制备量子点发光层进行配体交换，然后对膜的表面进行 乙醚清洗，再置于100℃下退火20min；
在量子点发光层上依次制备空穴传输层、空穴注入层和顶电极。
其中，所述衬底为玻璃基底；底电极为Al，厚度为50nm；所述电子传输层为ZnO，厚度为60nm；量子点发光层为InP/ZnS，厚度为100nm；空穴传输层为TFB，厚度为80nm；空穴注入层为PEDOT:PSS，厚度为40nm；顶电极为ITO，厚度为100nm。
综上所述，本公开提供一种量子点发光二极管及其制备方法。本公开通过在制备量子点发光二极管过程中，先在基板表面蒸镀一层短链配体化合物，然后制备量子点发光层，即可完成量子点发光层的单侧配体交换。该方式有利于电子和空穴在量子点发光层进行复合，减少非辐射跃迁的发生，从而大大提高发光效率。同时，与现有配体交换方法相比，本公开配体交换方法具有步骤简单、操作时间短、且能有效的避免对其他膜层的影响等优点。进一步地，本公开还可继续在量子点发光层表面蒸镀一层长链配体化合物，即可完成量子点发光层另一侧配体交换。该方式可以进一步地利于电子和空穴在量子点发光层进行复合，减少非辐射跃迁的发生，从而大大提高发光效率。同时，该方法同样具有步骤简单、操作时间短、且能有效的避免对其他膜层的影响等优点。
应当理解的是，本公开的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本公开所附权利要求的保护范围。

Claims (20)

  1. 一种量子点发光二极管的制备方法，所述量子点发光二极管为正型器件，其特征在于，包括步骤：
    提供阳极；
    在所述阳极表面形成空穴功能层；
    在所述空穴功能层表面形成一层短链配体化合物；
    在所述短链配体化合物表面形成量子点发光层。
  2. 根据权利要求1所述的量子点发光二极管的制备方法，其特征在于，采用真空蒸镀的方法在所述空穴功能层表面沉积一层短链配体化合物。
  3. 根据权利要求1所述的量子点发光二极管的制备方法，其特征在于，在所述短链配体化合物表面形成量子点发光层之后，还包括步骤：采用真空蒸镀的方法在所述量子点发光层表面沉积一层长链配体化合物。
  4. 根据权利要求2所述的量子点发光二极管的制备方法，其特征在于，所述采用真空蒸镀的方法在所述空穴功能层表面沉积一层短链配体化合物的条件：蒸镀的温度为50-200℃，和/或蒸镀的时间为1-60min。
  5. 根据权利要求3所述的量子点发光二极管的制备方法，其特征在于，所述采用真空蒸镀的方法在所述量子点发光层表面沉积一层长链配体化合物的条件：蒸镀的温度为50-200℃，和/或蒸镀的时间为1-60min。
  6. 根据权利要求1所述的量子点发光二极管的制备方法，其特征在于，所述短链配体化合物选自主链碳原子数小于8的硫醇、硫酚、含硫的盐、碳原子数为2-10的有机胺和卤化物中的一种或多种。
  7. 根据权利要求6所述的量子点发光二极管的制备方法，其特征在于，所述主链碳原子数小于8的硫醇选自3-巯基丙酸、巯基乙醇、巯基己醇、丙二硫醇、2-巯基-3丁醇、1，2-乙烷二硫醇、1,6-己二硫醇、1，4-二巯基-2，3-丁二醇、6-巯基己醇、半胱氨酸、丙烷-1,2,3-三硫醇和2，3-二巯基-1-丙硫醇中的一种或多种；和/或
    所述硫酚选自苯硫醇、1，2-苯二硫醇、1，3-苯二硫醇和1，4-苯二硫醇中的一种或多种；和/或
    所述含硫的盐包括硫氰酸铵、硫化铵、二硫代氨基甲酸酯和二硫代氨基甲酸锌中的一种或多种；和/或
    所述碳原子数为2-10的有机胺选自正辛胺、癸胺、1，2-乙二胺和二乙氨基乙醇中的一种或多种；和/或
    所述卤化物选自HF、NH 4F、HCl、NH 4Cl、HBr、NH 4Br、LiF、KF、NaF、BeF 2、MgF 2、CaF 2、AlF 3、InF 3、LiCl、NaCl、MgCl 2、CaCl 2、ZnCl 2、AlCl 3、GaCl 3、InCl 3、LiBr、NaBr、MgBr 2、CaBr 2、ZnBr 2、AlBr 3、GaBr 3、InBr 3、LiI、NaI、MgI 2、CaI 2、ZnI 2、AlBr 3、GaI 3、InI 3、碘化四丁基铵、溴化四丁基铵、氯化四丁基铵和氟化四丁基铵中的一种或多种。
  8. 根据权利要求3所述的量子点发光二极管的制备方法，其特征在于，所述长链配体化合物选自主链碳原子数大于等于8的硫醇和含氨基的聚合物中的一种或两种。
  9. 根据权利要求8所述的量子点发光二极管的制备方法，其特征在于，所述主链碳原子数大于等于8的硫醇选自辛基硫醇、十二烷基硫醇、叔-十二硫醇、1,8-辛二硫醇11-巯基十一醇、11-巯基十一烷酸、1,8-二巯基-3,6-二硫杂辛烷、6，8-二巯基辛酸、十二烷基硫醇锌聚合物和三聚硫氰酸中的一种或多种；和/或
    所述含氨基的聚合物选自聚(酰氨基胺)树枝状大分子、聚醚胺和氨基硅酮中的一种或多种。
  10. 根据权利要求1所述的量子点发光二极管的制备方法，其特征在于，采用溶液法在所述空穴功能层表面沉积一层短链配体化合物。
  11. 一种量子点发光二极管的制备方法，所述量子点发光二极管为反型器件，其特征在于，包括步骤：
    提供阴极；
    在所述阴极表面形成电子功能层；
    在所述电子功能层表面形成一层短链配体化合物；
    在所述短链配体化合物表面形成量子点发光层。
  12. 根据权利要求11所述的量子点发光二极管的制备方法，其特征在于，采用真 空蒸镀的方法在所述电子功能层表面沉积一层短链配体化合物。
  13. 根据权利要求11所述的量子点发光二极管的制备方法，其特征在于，在所述短链配体化合物表面形成量子点发光层之后，还包括步骤：采用真空蒸镀的方法在所述量子点发光层表面沉积一层长链配体化合物。
  14. 根据权利要求12所述的量子点发光二极管的制备方法，其特征在于，所述采用真空蒸镀的方法在所述电子功能层表面沉积一层短链配体化合物的条件：蒸镀的温度为50-200℃，和/或蒸镀的时间为1-60min。
  15. 根据权利要求13所述的量子点发光二极管的制备方法，其特征在于，所述采用真空蒸镀的方法在所述量子点发光层表面沉积一层长链配体化合物的条件：蒸镀的温度为50-200℃，和/或蒸镀的时间为1-60min。
  16. 根据权利要求11所述的量子点发光二极管的制备方法，其特征在于，所述短链配体化合物选自主链碳原子数小于8的硫醇、硫酚、含硫的盐、碳原子数为2-10的有机胺和卤化物中的一种或多种。
  17. 根据权利要求16所述的量子点发光二极管的制备方法，其特征在于，所述主链碳原子数小于8的硫醇选自3-巯基丙酸、巯基乙醇、巯基己醇、丙二硫醇、2-巯基-3丁醇、1，2-乙烷二硫醇、1,6-己二硫醇、1，4-二巯基-2，3-丁二醇、6-巯基己醇、半胱氨酸、丙烷-1,2,3-三硫醇和2，3-二巯基-1-丙硫醇中的一种或多种；和/或
    所述硫酚选自苯硫醇、1，2-苯二硫醇、1，3-苯二硫醇和1，4-苯二硫醇中的一种或多种；和/或
    所述含硫的盐包括硫氰酸铵、硫化铵、二硫代氨基甲酸酯和二硫代氨基甲酸锌中的一种或多种；和/或
    所述碳原子数为2-10的有机胺选自正辛胺、癸胺、1，2-乙二胺和二乙氨基乙醇中的一种或多种；和/或
    所述卤化物选自HF、NH 4F、HCl、NH 4Cl、HBr、NH 4Br、LiF、KF、NaF、BeF 2、MgF 2、CaF 2、AlF 3、InF 3、LiCl、NaCl、MgCl 2、CaCl 2、ZnCl 2、AlCl 3、GaCl 3、InCl 3、LiBr、NaBr、MgBr 2、CaBr 2、ZnBr 2、AlBr 3、GaBr 3、InBr 3、LiI、NaI、MgI 2、CaI 2、ZnI 2、 AlBr 3、GaI 3、InI 3、碘化四丁基铵、溴化四丁基铵、氯化四丁基铵和氟化四丁基铵中的一种或多种。
  18. 根据权利要求13所述的量子点发光二极管的制备方法，其特征在于，所述长链配体化合物选自主链碳原子数大于等于8的硫醇和含氨基的聚合物中的一种或两种。
  19. 根据权利要求18所述的量子点发光二极管的制备方法，其特征在于，所述主链碳原子数大于等于8的硫醇选自辛基硫醇、十二烷基硫醇、叔-十二硫醇、1,8-辛二硫醇、11-巯基十一醇、11-巯基十一烷酸、1,8-二巯基-3,6-二硫杂辛烷、6，8-二巯基辛酸、十二烷基硫醇锌聚合物和三聚硫氰酸中的一种或多种；和/或
    所述含氨基的聚合物选自聚(酰氨基胺)树枝状大分子、聚醚胺和氨基硅酮中的一种或多种。
  20. 根据权利要求11所述的量子点发光二极管的制备方法，其特征在于，采用溶液法在所述电子功能层表面形成一层短链配体化合物。
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