WO2019010997A1 - 发光二极管及其制备方法 - Google Patents

发光二极管及其制备方法 Download PDF

Info

Publication number
WO2019010997A1
WO2019010997A1 PCT/CN2018/079467 CN2018079467W WO2019010997A1 WO 2019010997 A1 WO2019010997 A1 WO 2019010997A1 CN 2018079467 W CN2018079467 W CN 2018079467W WO 2019010997 A1 WO2019010997 A1 WO 2019010997A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
layer
light emitting
emitting diode
substrate
Prior art date
Application number
PCT/CN2018/079467
Other languages
English (en)
French (fr)
Inventor
曹蔚然
梁柱荣
刘佳
Original Assignee
Tcl集团股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tcl集团股份有限公司 filed Critical Tcl集团股份有限公司
Publication of WO2019010997A1 publication Critical patent/WO2019010997A1/zh

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
    • H01L33/40—Materials therefor
    • 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
    • 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
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing

Definitions

  • the invention belongs to the technical field of light-emitting diodes, and in particular to a light-emitting diode (light-emitting diode) and a preparation method thereof.
  • the most promising production process for large-scale industrialization is ink printing.
  • Conventional printed thin-film light-emitting diodes generally print a luminescent layer ink or other functional layer ink onto a strip-shaped groove substrate with an array, and the solvent is evaporated to deposit a film.
  • the formulation of the luminescent layer ink or the functional layer ink, the quality of the printing substrate, the accuracy of the printing device, etc. all have a crucial influence on the uniformity of the film layer, and it is easy to cause a "coffee ring".
  • the substrate used for printing thin film light-emitting diodes is complicated in structure, complicated in manufacturing process, large in environmental pollution, and its structural shape is not completely conducive to deposition of the film layer, and at the same time, the substrate material, the substrate thickness and the concave surface. Factors such as the height of the edge of the groove make the product thicker and are not conducive to making a flexible device.
  • the quantum dot light-emitting diode since the quantum dot has a larger particle size than ordinary particles or small organic molecules, and the quantum dot surface is rich in organic ligands, the connection between the quantum dot particles after film formation is not tight, and the film layer is not dense.
  • a light emitting diode comprising an oppositely disposed substrate and a top electrode, the substrate comprising a substrate and a bottom electrode disposed on the substrate, and the bottom electrode and the top electrode Provided with a light-emitting layer, the light-emitting diode further comprising a graphene layer for anchoring adjacent functional layers, and the surface of the graphene layer is modified with a first reactive functional group;
  • the substrate is a groove substrate
  • the bottom electrode is a first graphene electrode
  • the graphene layer is a graphene layer laminated on the bottom electrode
  • the graphene layer is patterned a graphene layer
  • the first reactive functional group is modified on a surface of the graphene layer facing the light emitting layer, and the patterned graphene layer is adjacent to the bottom electrode by the first reactive functional group Functional layer combination;
  • the light emitting diode is a quantum dot light emitting diode device
  • the light emitting layer is a quantum dot light emitting layer
  • the graphene layer is a graphene pixel array disposed between the quantum dot emitting layer and the bottom electrode, and
  • the quantum dot light-emitting layer is bonded to the graphene pixel array through the first reactive functional group.
  • the substrate including a substrate and a bottom electrode disposed on the substrate, transferring the graphene pixel array onto the bottom electrode, and causing the graphene pixel to face away from the bottom electrode
  • the surface of the array is modified to modify the first reactive functional group
  • a quantum dot luminescent layer is sequentially deposited on the graphene pixel array.
  • the light emitting diode provided by the invention comprises a graphene layer, and the surface of the graphene layer is modified with a first reactive functional group, and the graphene layer can anchor adjacent functions through the first reactive functional group of the surface Layers to form a flat, strong film layer.
  • the light emitting diode is a quantum dot light emitting diode device
  • the graphene layer is a graphene pixel array disposed between the quantum dot emitting layer and the bottom electrode
  • passing through the graphene pixel array surface a reactive functional group, which can closely anchor quantum dots in the quantum dot luminescent layer to the surface of the graphene pixel array, thereby forming a dense and uniform quantum dot luminescent layer, thereby preventing deposition in a subsequent functional layer It is dissolved or washed away by the solvent to improve the film formation uniformity of the quantum dot light-emitting layer.
  • the graphene pixel array is capable of providing a printing site (ie, a region covered with functionalized graphene capable of anchoring a quantum dot, while a quantum dot not covering the functionalized graphene region cannot be retained by subsequent solvent rinsing Therefore, it is possible to replace the complicated and thick printing groove which is currently used.
  • the graphene pixel array is used as a printing site, and the number, distance, and the like of the pixel points can be flexibly adjusted by adjusting the pattern of the graphene layer, thereby improving printing flexibility and printing efficiency, and being suitable for preparing a thinner and lighter display. panel.
  • the graphene layer is a patterned graphene layer laminated on the bottom electrode, and the first reactive functional group is modified when the graphene layer faces a surface of the light emitting layer
  • the The patterned graphene layer can provide printing sites for printed thin film light emitting diodes, facilitating deposition of functional layers.
  • the graphene bottom electrode can be directly used as a conductive electrode of a printed thin film light emitting diode, and on the basis of the above, the patterned graphene layer can be formed as a hole transport layer. Since the patterned graphene layer is rich in reactive functional groups, the reactive functional groups can effectively anchor the further deposited luminescent material to form a uniform luminescent layer.
  • the region not covering the patterned graphene layer cannot be anchored by the luminescent material, and can be easily removed by solvent cleaning or the like during the deposition process of the subsequent functional layer, thereby finally obtaining high resolution, high efficiency, and high uniformity.
  • the method for preparing a light emitting diode device provided by the present invention, by transferring a graphene pixel array onto a bottom electrode, and then depositing a quantum dot on a surface of the graphene pixel array modified with a functional functional group, so that the quantum dot can pass the
  • the reactive functional groups are effectively anchored on the graphene pixel array to form a dense and uniform quantum dot luminescent layer, which improves film formation uniformity.
  • the use of the graphene pixel array as a printing site can simplify the fabrication process of the LED device.
  • the quantum dots deposited by the off-site can be removed by cleaning, thereby improving the quality of the film layer, thereby facilitating the performance improvement of the light-emitting diode device.
  • the light emitting diode device provided by the invention has excellent light emission uniformity, good luminous efficiency and device stability, and good structural design flexibility.
  • FIG. 1 is a schematic diagram of a preparation process of a light emitting diode device according to an embodiment of the present invention.
  • Embodiments of the present invention provide a light emitting diode including an oppositely disposed substrate and a top electrode, the substrate including a substrate and a bottom electrode disposed on the substrate, and between the bottom electrode and the top electrode A light emitting layer is provided, the light emitting diode further comprising a graphene layer for anchoring adjacent functional layers, and the surface of the graphene layer is modified with a first reactive functional group.
  • the first reactive functional group has better reactivity, and is beneficially bonded to an adjacent functional layer such as a light-emitting layer, an electron or a hole functional layer material, thereby effectively forming a printing site of the light emitting diode.
  • an adjacent functional layer such as a light-emitting layer, an electron or a hole functional layer material
  • the first reactive functional group may be connected to a ligand on the surface of the quantum dot, or may be directly connected to the quantum dot, and the double anchor quantifies the sub-point, thereby The quantum dots are effectively immobilized on the surface of the graphene pixel array.
  • the preferred reactive functional groups can also be attached to the surface defects of the quantum dots, and at the same time act to passivate the surface defects of the quantum dots, further improving the device efficiency.
  • the first reactive functional groups in the quantum dot light emitting diode are -OH, -COOH, -NH 2 , -NH-, -SH, -CN, -SO 3 H, -SOOH, -NO 2 , - At least one of CONH 2 , -CONH-, -COCl, -CO-, -CHO, -Cl, -Br.
  • the substrate is a groove substrate
  • the bottom electrode is a first graphene electrode
  • the graphene layer is a graphene layer laminated on the bottom electrode
  • the graphene The layer is a patterned graphene layer
  • the first reactive functional group is modified on a surface of the graphene layer facing the light emitting layer, and the patterned graphene layer passes through the first reactive functional group and faces the bottom
  • the adjacent functional layers of the electrodes are combined.
  • the first graphene electrode and the patterned graphene layer disposed on the substrate together form a patterned composite layer to form a pixel array of the printed thin film LED.
  • the first graphene electrode can serve as a conductive electrode
  • the patterned graphene layer functions as a hole transport layer, and when the light emitting layer is deposited thereon, since the second patterned graphene layer faces the The surface of the luminescent layer is modified with a reactive functional group, so that the luminescent layer material can be effectively anchored (the region not covering the second patterned graphene layer is not luminescent material, and can be cleaned by solvent during deposition of the subsequent functional layer).
  • the method can be easily removed, which is beneficial to improve the film formation uniformity of the light-emitting layer, thereby improving the performance of the light-emitting diode, especially the printed film light-emitting diode.
  • the first graphene electrode may be an entire layer of graphene layer, or may be patterned.
  • the pattern of the first graphene electrode is consistent with the pattern of the patterned graphene layer, and both achieve complete overlap.
  • the first graphene electrode is a single layer graphene or a multilayer graphene, preferably a single layer graphene.
  • the patterned graphene layer is a single layer graphene or a multilayer graphene.
  • the patterned graphene layer has a work function ranging from 4.8 eV to 5.2 eV, which imparts excellent hole transport properties to the patterned graphene layer, thereby matching different quantum dot luminescent materials to better realize energy. Match it to improve its performance.
  • the embodiment of the invention can adjust the forbidden band width by adjusting the degree of oxidation of the graphene, the type of surface functional groups, the type of doping ions, and the like, thereby adjusting the hole transporting capacity.
  • the light emitting diode is a quantum dot light emitting diode
  • the light emitting layer is a quantum dot light emitting layer
  • the graphene layer is graphite disposed between the quantum dot emitting layer and the bottom electrode.
  • An olefin pixel array, and the quantum dot luminescent layer is combined with the graphene pixel array by the first reactive functional group.
  • the quantum dot light emitting diode may be a positive quantum dot light emitting diode or an inverse quantum dot light emitting diode.
  • the quantum dot light emitting diode is a positive quantum dot light emitting diode, that is, the bottom electrode is an anode, and the top electrode is a cathode.
  • a hole injection layer and/or a hole transport layer are disposed between the anode and the quantum dot light-emitting layer, and an electron injection layer and/or an electron is disposed between the cathode and the quantum dot light-emitting layer. Transport layer.
  • the quantum dot light emitting diode is an inverse quantum dot light emitting diode, that is, the bottom electrode is a cathode and the top electrode is an anode. Further, an electron injection layer and/or an electron transport layer is disposed between the cathode and the quantum dot light-emitting layer, and a hole injection layer and/or a hole is disposed between the anode and the quantum dot light-emitting layer. Transport layer.
  • the surface of the graphene pixel array is modified with the first reactive functional group, and the first reactive functional group is modified on a surface of the graphene pixel array facing away from the bottom electrode, In order to achieve the combination with the quantum dot luminescent layer.
  • the pattern of the graphene pixel array is not strictly limited, and may be designed to have an array pattern of any size and arbitrary shape; and the size of the pixel point and the shape of the pixel point in the graphene pixel array The spacing between pixels and the combination of pixel points can be flexibly designed.
  • the graphene pixel array has a thickness of 1-150 nm. If the thickness of the graphene pixel array is too thin, the amount of the first reactive functional group is too small, and the anchoring of the quantum dots cannot be sufficiently achieved; if the thickness of the graphene pixel array is too thick, exciton recombination is difficult. Reduce the luminous efficiency of the device. Further preferably, the graphene pixel array has a thickness of 5 to 50 nm, thereby achieving close integration of the quantum dot light-emitting layer and the graphene pixel array while achieving good luminous efficiency.
  • a hydrophobic oxygen barrier layer is disposed between the array of graphene pixel arrays (ie, regions not covered with functionalized graphene).
  • the hydrophobic oxygen-absorbing insulating layer can play the role of a separator when depositing the quantum dot light-emitting layer and other functional layers, and isolate each pixel point, thereby improving the deposition quality of each functional layer.
  • the thickness of the hydrophobic oxygen barrier layer can be very thin compared to a conventional separator, so that an ultrathin printed quantum dot light emitting diode can be prepared.
  • the hydrophobic oxygen barrier layer has the characteristics of hydrophobic oxygen barrier, thereby effectively preventing residual quantum dots in the non-pixel dot region due to deposition deviation, improving the waterproof and oxygen resistance performance of the quantum dot light emitting diode, and improving the printed quantum dot light emitting diode. Resolution and lifetime.
  • the hydrophobic oxygen barrier layer is made of a hydrophobic oxygen-absorbing organic substance and/or a hydrophobic oxygen-free inorganic substance.
  • the hydrophobic oxygen-repellent organic material comprises polymethyl methacrylate, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polybutylene terephthalate, ethylene terephthalate. , at least polyimide, nitrile rubber, chlorobenzene rubber, polyvinyl alcohol, polycarbonate, polyetheretherketone, polyethersulfone, polyarylate, polyarylate, polyvinylpyrrolidone, silicone One, but not limited to.
  • the hydrophobic oxygen-absorbing inorganic substance is at least one of silica, alumina, zirconia, and magnesia, but is not limited thereto. The preferred hydrophobic oxygen barrier material can better achieve the above properties.
  • the bottom electrode is a patterned second graphene electrode.
  • the second graphene electrode may be selected the same as the first graphene electrode.
  • the surface of the second graphene electrode is provided with a hydrophobic layer, and the surface of the second graphene electrode is modified with a second active functional group, the hydrophobic material in the hydrophobic layer and the second The reactive functional groups are bonded to bond to firmly bond the second graphene electrode to form a patterned hydrophobic region (ie, a patterned composite layer) that encloses the pixel array recess.
  • the inner wall of the pixel array groove (the portion where the hydrophobic layer is not deposited) and the bottom portion provided by the embodiment of the present invention are not subjected to hydrophobic treatment, and therefore have affinity for the printing ink, which is favorable for deposition of each functional layer.
  • the patterned composite layer for isolating the pixel array is subjected to surface hydrophobic treatment, the ink cannot be effectively wetted and formed during the printing process, thereby preventing cross-coloring when printing the functional layer, and effectively improving the printing of the light-emitting diode. Performance, which in turn improves device uniformity and device stability.
  • the LED substrate provided by the embodiment of the invention can meet the requirements of various ultra-thin rigid or flexible devices, simplify the process complexity, and improve the plasticity of the thin-film LED structure.
  • the second graphene electrode is modified with a second active functional group on the surface of the substrate.
  • the second reactive functional group can be bonded to the hydrophobic material to firmly bond the hydrophobic layer to the patterned graphene layer; and other regions than the second graphene electrode are not provided
  • the graphene which is the second surface active functional group cannot be combined with the hydrophobic material and has no hydrophobic property, and can ensure smooth printing of each functional layer. Thereby, the printing performance of the thin film LED substrate for printing is improved.
  • the graphene in the second graphene electrode is not strictly limited, and may be a single layer graphene or a multilayer graphene.
  • the second reactive functional group is -OH, -COOH, -NH 2 , -NH-, -SH, -CN, -SO 3 H, -SOOH, -NO 2 , -CONH 2 , -CONH-, At least one of -COCl, -CO-, -CHO, -Cl, -Br, but is not limited thereto.
  • the second reactive functional group has better reactivity and is advantageous for binding to the hydrophobic material.
  • the hydrophobic material is an organic polymer compound.
  • the organic polymer compound is polymethyl methacrylate, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polybutylene terephthalate, polyethylene terephthalate.
  • the organic polymer compound has not only good hydrophobic properties but also a patterned hydrophobic region, and the organic polymer compound has a higher activity with the second reactive functional group, particularly preferably the second reactive functional group.
  • Good reactivity is beneficial to the fixation of hydrophobic materials and the formation of hydrophobic regions.
  • the substrate used in the embodiment of the present invention may be a rigid substrate or a flexible substrate.
  • the substrate is a rigid substrate or a flexible substrate, wherein the rigid substrate comprises glass or a metal foil; the flexible substrate comprises polyethylene terephthalate or polyethylene terephthalate. Ester, polyetheretherketone, polystyrene, polyethersulfone, polycarbonate, polyarylate, polyarylate, polyimide, polyvinyl chloride, polyethylene, polyvinylpyrrolidone, textile fiber.
  • the anode can be selected from conventional anode materials in the field of quantum dot light emitting diodes.
  • the anode is a doped metal oxide including, but not limited to, indium doped tin oxide (ITO), fluorine doped tin oxide (FTO), antimony doped tin oxide.
  • ITO indium doped tin oxide
  • FTO fluorine doped tin oxide
  • ATO aluminum-doped zinc oxide
  • GZO gallium-doped zinc oxide
  • IZO indium-doped zinc oxide
  • MZO magnesium-doped zinc oxide
  • AMO aluminum-doped magnesium oxide
  • the anode is a composite electrode containing a metal interlayer in a transparent metal oxide, wherein the transparent metal oxide may be a doped transparent metal oxide or an undoped transparent metal oxide. Things.
  • the composite electrode includes, but is not limited to, AZO/Ag/AZO, AZO/Al/AZO, ITO/Ag/ITO, ITO/Al/ITO, ZnO/Ag/ZnO, ZnO/Al/ZnO, TiO 2 /Ag/TiO 2 , one or more of TiO 2 /Al/TiO 2 , ZnS/Ag/ZnS, ZnS/Al/ZnS, TiO 2 /Ag/TiO 2 , TiO 2 /Al/TiO 2 .
  • the hole injection layer is selected from an organic material having a hole injecting ability.
  • the hole injecting material for preparing the hole injecting layer includes, but not limited to, poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS), copper phthalocyanine (CuPc), 2,3, 5,6-tetrafluoro-7,7',8,8'-tetracyanoquinone-dimethane (F4-TCNQ), 2,3,6,7,10,11-hexacyano-1,4,5 , one or more of 8,9,12-hexaazatriphenylene (HATCN), doped or undoped transition metal oxide, doped or undoped metal sulfur-based compound.
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid
  • CuPc copper phthalocyanine
  • F4-TCNQ 2,3, 5,6-tetrafluoro-7,7
  • the transition metal oxide includes, but is not limited to, at least one of MoO 3 , VO 2 , WO 3 , CrO 3 , CuO;
  • the metal sulfur-based compound includes, but not limited to, MoS 2 , MoSe 2 , WS 2 , At least one of WSe 2 and CuS.
  • the hole transport layer is selected from organic materials having hole transporting ability, including but not limited to poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB) , polyvinyl carbazole (PVK), poly(N, N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine) (poly-TPD), poly(9,9- Dioctyl fluorene-co-bis-N,N-phenyl-1,4-phenylenediamine) (PFB), 4,4',4''-tris(carbazol-9-yl)triphenylamine (TCTA) , 4,4'-bis(9-carbazole)biphenyl (CBP), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-linked Benzene-4,4'-diamine (TP
  • the hole transport layer 4 is selected from inorganic materials having hole transporting ability, including but not limited to doped or undoped MoO 3 , VO 2 , WO 3 , CrO 3 , CuO, MoS. 2. At least one of MoSe 2 , WS 2 , WSe 2 , and CuS.
  • the quantum dot luminescent layer is made of a conventional quantum dot, and the quantum dot may be a II-VI nanocrystal, a III-V nanocrystal, a II-V nanocrystal, a III-VI nanocrystal, an IV- One or more of Group VI nanocrystals, Group I-III-VI nanocrystals, Group II-IV-VI nanocrystals or Group IV elements.
  • the II-VI nanocrystals include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, but are not limited thereto, and may be other binary, ternary
  • the quaternary II-VI nanocrystals; the III-V group nanocrystals include GaP, GaAs, InP, InAs, but are not limited thereto, and may be other binary, ternary, and quaternary III-V compounds.
  • the quantum dots are doped or undoped inorganic perovskite semiconductors, and/or organic-inorganic hybrid perovskite semiconductors.
  • the inorganic perovskite semiconductor has a structural formula of AMX 3 , wherein A is a Cs + ion, and M is a divalent metal cation, including but not limited to Pb 2+ , Sn 2+ , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ , X are halogen anions, including but not limited to Cl - , Br - , I - .
  • the organic-inorganic hybrid perovskite semiconductor has the structural formula BMX 3 , wherein B is an organic amine cation including, but not limited to, CH 3 (CH 2 ) n-2 NH 3 + (n ⁇ 2) or NH 3 (CH 2 ) n NH 3 2+ (n ⁇ 2).
  • B is an organic amine cation including, but not limited to, CH 3 (CH 2 ) n-2 NH 3 + (n ⁇ 2) or NH 3 (CH 2 ) n NH 3 2+ (n ⁇ 2).
  • B is an organic amine cation including, but not limited to, CH 3 (CH 2 ) n-2 NH 3 + (n ⁇ 2) or NH 3 (CH 2 ) n NH 3 2+ (n ⁇ 2).
  • the three-dimensional structure; when n>2, the inorganic metal halide octahedron MX 6 4- connected in a co-top manner extends in a two-dimensional direction to form a layered structure, intercalated with an organic amine cation bilayer (protonated single) An amine) or an organic amine cation monolayer (protonated bisamine), the organic layer and the inorganic layer overlap each other to form a stable two-dimensional layered structure;
  • M is a divalent metal cation, including but not limited to Pb 2+ , Sn 2 + , Cu 2+ , Ni 2+ , Cd 2+ , Cr 2+ , Mn 2+ , Co 2+ , Fe 2+ , Ge 2+ , Yb 2+ , Eu 2+ ,
  • X are halogen anions, including but not Limited to Cl - , Br - , I - .
  • the electron transport layer is selected from materials having electron transport properties, preferably metal oxides having electron transport properties including, but not limited to, n-type ZnO, TiO 2 , SnO 2 , Ta 2 O 3 , AlZnO. At least one of ZnSnO, InSnO, Alq 3 , Ca, Ba, CsF, LiF, and CsCO 3 .
  • the cathode is one or more of various conductive carbon materials, conductive metal oxide materials, and metal materials.
  • the conductive carbon material includes, but is not limited to, doped or undoped carbon nanotubes, doped or undoped graphene, doped or undoped graphene oxide, C60, graphite, carbon fiber, long carbon, Or a mixture thereof;
  • the conductive metal oxide material includes, but is not limited to, ITO, FTO, ATO, AZO, or a mixture thereof;
  • the metal materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or alloy.
  • the form thereof includes, but not limited to, a nanosphere, a nanowire, a nanorod, a nanocone, a nano hollow sphere, or a mixture thereof.
  • the cathode is Ag or Al.
  • the light emitting diode of the embodiment of the invention further comprises an interface modifying layer, wherein the interface modifying layer is at least one of an electron blocking layer, a hole blocking layer, an electrode modifying layer and an isolating protective layer.
  • the package of the light emitting diode may be partially packaged, fully packaged, or not packaged, and is not strictly limited in the embodiment of the present invention.
  • the light emitting diode may be a partially packaged light emitting diode, a full package light emitting diode or a non-packaged light emitting diode.
  • the quantum dot light emitting diode provided by the embodiment of the present invention can be obtained by the following method.
  • the embodiment of the invention further provides a method for preparing a light emitting diode, wherein the light emitting diode is a quantum dot light emitting diode, comprising the following steps:
  • the method of depositing the graphene layer is not specifically limited as long as a uniform coverage of the graphene layer can be obtained.
  • the graphene layer is patterned to form a graphene pixel array, preferably a photolithography method, but is not limited thereto.
  • the graphene layer is patterned by photolithography to form a graphene pixel array.
  • the design of the graphene pixel array can be flexibly designed as described above, and is not described herein again in order to save space.
  • At least one surface of the graphene pixel array is modified to modify the surface of the graphene pixel array with a first reactive functional group, preferably by chemical treatment and/or physical treatment with a strong acid.
  • Surface modification is performed on at least one surface of the graphene pixel array by chemical treatment and/or physical treatment to introduce a large amount of the first reactive functional group.
  • the chemical treatment is at least one of an acid treatment, an alkali treatment, an electrochemical treatment, and a photochemical treatment.
  • the physical treatment is at least one of plasma treatment, ultraviolet ozone treatment, laser treatment, and heat treatment.
  • the substrate is a groove substrate.
  • the groove substrate is prepared by:
  • the method of depositing the graphene layer on the substrate is not strictly limited, and direct deposition or transfer deposition may be employed.
  • the selection of the graphene in the embodiment of the present invention is not strictly limited, and a single layer of graphene or a multilayer graphene may be used.
  • the patterning treatment of the graphene material layer can be achieved by a physical method, preferably by an etching method.
  • the graphene material layer may be etched into a pattern having a predetermined pattern or an array of pixel dots by a plasma etching or a photolithography method.
  • the groove structure is formed by etching, and the etched area corresponds to form a pixel array area.
  • the surface of the graphene electrode facing away from the substrate is modified to have a second reactive functional group modified from the surface of the graphene electrode facing away from the substrate.
  • the surface of the graphene electrode facing away from the substrate is modified by chemical treatment and/or physical treatment, and the surface of the graphene electrode is modified with a second reactive functional group to obtain a graphite having a surface modified with a second reactive functional group.
  • the chemical treatment is at least one of acid treatment, alkali treatment, electrochemical treatment, and photochemical treatment
  • the physical treatment is at least one of plasma treatment, ultraviolet ozone treatment, laser treatment, and heat treatment.
  • the patterned graphene surface is activated with a strong acid to introduce a rich functional group to obtain patterned graphene oxide.
  • the reactive functional group formed by the modification treatment is selected as described above, and is not described herein again in order to save space.
  • the hydrophobic material is tightly bonded to the surface of the patterned graphene electrode to form a hydrophobic layer by bonding the second reactive functional group, thereby making the patterned region hydrophobic, and printing
  • the ink is not effectively wetted and filmed, thereby forming a pixel array recess that can be effectively printed into a film.
  • the substrate is a groove substrate, and the groove substrate is prepared by:
  • the selection of the substrate is not strictly selected, as described in detail above.
  • a method of depositing a graphene bottom electrode and a graphene layer on the substrate, respectively, is not strictly limited.
  • the graphene layer is subjected to surface modification treatment to form graphene oxide on the surface of the graphene layer to obtain a surface-modified graphene layer, that is, the surface of the graphene layer is modified with a first active functional group.
  • the graphene layer may be surface-modified by chemical treatment and/or physical treatment to modify the surface of the graphene layer with a reactive functional group.
  • the chemical treatment is at least one of acid treatment, alkali treatment, electrochemical treatment, and photochemical treatment; and the physical treatment is at least one of plasma treatment, ultraviolet ozone treatment, laser treatment, and heat treatment.
  • the graphene layer is surface-activated with a strong acid to introduce a rich functional group.
  • the reactive functional group formed by the modification treatment is selected as described above, and is not described herein again in order to save space.
  • the surface-modified graphene layer is transferred to the surface of the graphene bottom electrode by a transfer method to form a composite graphene layer.
  • the composite graphene layer is patterned according to a preset pixel array of the light emitting diode to obtain a patterned graphene layer bottom electrode and a patterned graphene layer to form a patterned composite layer.
  • the patterning process may be implemented by a physical method, preferably by an etching method.
  • the composite graphene layer may be etched into a pattern of a predetermined pixel array having a printed thin film light emitting diode by a plasma etching or a photolithography method.
  • the pattern is not limited, and may be a pattern having an arbitrary size and an arbitrary shape; the preset pixel array may have an arbitrary pixel point size, an arbitrary pixel dot shape, an arbitrary pixel dot interval, and an arbitrary pixel dot combination.
  • the substrate is a groove substrate, and the groove substrate is prepared by:
  • the selection of the substrate is not strictly selected, as described in detail above.
  • a method of depositing a graphene bottom electrode and a graphene layer on the substrate, respectively, is not strictly limited.
  • the graphene pixel array is transferred onto the bottom electrode, and the surface of the modification process is opposite to the bottom electrode, thereby facilitating the closeness of the quantum dot light-emitting layer and the work graphene pixel array. Combine.
  • a quantum dot luminescent layer is deposited on the graphene pixel array, and the quantum dots in the quantum dot luminescent layer are tightly bonded to the functionalized graphene pixels through the reactive functional group.
  • the bottom electrode is an anode
  • the top electrode is a cathode.
  • the bottom electrode is a cathode and the top electrode is an anode.
  • the hole injection layer and/or the hole transport layer are disposed between the graphene pixel array and the anode, and are disposed between the graphene pixel array and the quantum dot light-emitting layer. There is an electron transport layer.
  • the method of depositing the hole injection layer, the hole transport layer, the quantum dot light-emitting layer, and the electron transport layer is preferably a printing method, and specifically includes, but not limited to, an inkjet printing method, a roll coating method, a transfer method, a knife coating method, and a slit. Further, the coating method is an inkjet printing method.
  • the deposition of the bottom electrode and the top electrode may be performed by a chemical method or a physical method, wherein the chemical method includes, but not limited to, chemical vapor deposition, continuous ion layer adsorption and reaction, anodization, electrolytic deposition, and the like.
  • the physical methods include, but are not limited to, physical coating or solution processing, wherein the solution processing methods include, but are not limited to, spin coating, printing, knife coating, and immersion pulling , immersion method, spray method, roll coating method, casting method, slit coating method, strip coating method; physical coating method includes but not limited to thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method One or more of a multi-arc ion plating method, a physical vapor deposition method, an atomic layer deposition method, and a pulsed laser deposition method.
  • a method for preparing a positive-printed quantum dot light-emitting diode includes the following steps:
  • a graphene layer having a thickness of 20 nm is prepared on a copper sheet by a CVD method, and the graphene layer is transferred onto a silicon wafer, and the graphene layer is etched into a regular arrangement of graphene by photolithography.
  • the pixel array 4', the graphene on the surface of the graphene pixel array 4' is activated by concentrated sulfuric acid, and has a large amount of active functional groups on the surface thereof to obtain a graphene pixel array 4;
  • the CdSe/ZnS quantum dot light-emitting layer 5 and the ZnO electron transport layer 6 are sequentially printed on the graphene pixel array 4 by a printing method, and finally the Al cathode 7 is vapor-deposited to obtain a positive-printed quantum dot light-emitting diode.
  • a method for preparing an inverse printed quantum dot light emitting diode comprises the following steps:
  • a graphene layer having a thickness of 20 nm is prepared on the copper sheet by a CVD method, and the graphene layer is transferred onto the silicon wafer, and the graphene layer is etched into a regular arrangement of graphene by photolithography.
  • a pixel array wherein the graphene on the surface of the graphene pixel array is activated by concentrated sulfuric acid to have a large amount of active functional groups on the surface thereof to obtain a graphene pixel array;
  • a method for preparing a printed quantum dot light emitting diode comprises the following steps:
  • the composite graphene layer is plasma-etched to form a patterned composite layer to obtain a quantum dot light-emitting diode substrate for printing.
  • a method for preparing a printed organic light emitting diode comprises the following steps:
  • the composite graphene layer is plasma-etched to form a patterned composite layer to obtain an organic light-emitting diode substrate for printing.
  • a method for preparing a printed quantum dot light emitting diode device comprises the following steps:
  • the surface of the patterned graphene electrode is activated by concentrated sulfuric acid, and a reactive functional group is introduced to obtain a patterned graphene electrode; a polymethyl methacrylate layer is formed on the surface of the patterned graphene electrode to obtain a quantum dot illumination for printing. Diode substrate. Wherein the region not covered with graphene forms a pixel array recess.
  • a method for preparing a printed organic light emitting diode comprises the following steps:

Abstract

一种发光二极管，包括相对设置的衬底和顶电极，衬底包括基板和设置在基板上的底电极，且底电极和顶电极之间设置有发光层（5），发光二极管还包括用于锚定相邻功能层的石墨烯层，且石墨烯层的表面修饰有第一活性官能团；其中，衬底为凹槽衬底，底电极为第一石墨烯电极，石墨烯层为设置在底电极和发光层（5）之间的图案化石墨烯层，且第一活性官能团修饰在石墨烯层朝向所述发光层（5）的表面；或发光二极管为量子点发光二极管器件，发光层（5）为量子点发光层，石墨烯层为设置在量子点发光层（5）与底电极之间的石墨烯像素阵列，且量子点发光层（5）通过第一活性官能团与石墨烯像素阵列结合。

Description

发光二极管及其制备方法 技术领域
本发明属于发光二极管技术领域，尤其涉及一种发光二极管（发光二极管）及其制备方法。
 背景技术
近年来，随着科技的进步，显示技术取得了快速的发展。现代显示技术根据信息显示的主要方式分为阴极射线管（Cathode Ray Tube, CRT）和平板显示（Flat Panel Display, FPD）。目前市场上，传统的CRT技术已基本在显示技术历史舞台上淡出，而各种新型的平板显示技术逐渐兴起。在平板显示技术中，发光二极管（Light Emitting Diode, LED）与液晶显示技术（Liquid Crystal Display, LCD）相比，在色彩表现、节约能源等方面具有突出的优势，成为具有巨大发展潜力的新型显示技术，其中，目前研究最多且发展前景最大的发光二极管主要包括有机发光二极管（Organic Light Emitting Diode, OLED）和量子点发光二极管（Quantum Dot Light Emitting Diode, QLED）。
对于薄膜发光二极管，特别是有机发光二极管和量子点发光二极管，目前最有希望实现大规模产业化的生产工艺是墨水打印法。传统的印刷型薄膜发光二极管，一般是将发光层墨水或其他功能层墨水打印到带有阵列的条形凹槽衬底上，溶剂挥发后沉积成薄膜。然而，在打印过程中，发光层墨水或功能层墨水的配方、印刷用衬底的质量、打印设备的精确度等都对膜层的均匀性有至关重要的影响，极易造成“咖啡环”等成膜不均匀等现象。除此之外，目前印刷薄膜发光二极管所用的衬底结构复杂、制作工艺复杂、对环境污染大、且其结构形状并不完全利于膜层的沉积，同时，衬底材料、衬底厚度和凹槽边缘的高度等因素会使产品厚度较大，且不利于做成柔性器件。此外，量子点发光二极管中，由于量子点的颗粒尺寸较普通粒子或有机小分子大，并且量子点表面含有丰富的有机配体，成膜后量子点颗粒之间的连接并不紧密，膜层相对松散，同时与其下方的空穴传输层之间紧密度低，膜层相对松散，沉积后的量子点仍有很大机会在后续其他功能层的溶液法成膜过程中重新溶解带走或直接冲走，导致量子点膜层不均匀、界面缺陷较大，进而导致器件发光不均匀。即使采用难溶解量子点的溶剂，也难以避免该过程的发生，而且也因为这样，后续功能层材料的选择也会受到其可选溶剂的限制。
 技术问题
本发明的目的在于提供一种发光二极管及其制备方法，旨在解决现有发光二极管成膜均匀性差导致器件发光不均匀的问题。
 技术解决方案
本发明是这样实现的，一种发光二极管，包括相对设置的衬底和顶电极，所述衬底包括基板和设置在所述基板上的底电极，且所述底电极和所述顶电极之间设置有发光层，所述发光二极管还包括用于锚定相邻功能层的石墨烯层，且所述石墨烯层的表面修饰有第一活性官能团；
其中，所述衬底为凹槽衬底，所述底电极为第一石墨烯电极，所述石墨烯层为层叠结合在所述底电极上的石墨烯层，所述石墨烯层为图案化石墨烯层，且所述第一活性官能团修饰在所述石墨烯层朝向所述发光层的表面，所述图案化石墨烯层通过所述第一活性官能团与背对所述底电极的相邻功能层结合；
或
所述发光二极管为量子点发光二极管器件，所述发光层为量子点发光层，所述石墨烯层为设置在所述量子点发光层与所述底电极之间的石墨烯像素阵列，且所述量子点发光层通过所述第一活性官能团与所述石墨烯像素阵列结合。
以及，一种发光二极管的制备方法，所述发光二极管为量子点发光二极管，包括以下步骤：
沉积石墨烯层，对所述石墨烯层进行图案化处理形成石墨烯像素阵列，对所述石墨烯像素阵列的至少一表面进行修饰处理，使所述石墨烯像素阵列表面修饰有第一活性官能团，得到石墨烯像素阵列；
提供衬底，所述衬底包括基板和设置在所述基板上的底电极，将所述石墨烯像素阵列转印到所述底电极上，且使得背对所述底电极所述石墨烯像素阵列的表面经过修饰处理修饰有所述第一活性官能团；
在所述石墨烯像素阵列上依次沉积量子点发光层。
 有益效果
本发明提供的发光二极管，包括用于石墨烯层，且所述石墨烯层的表面修饰有第一活性官能团，所述石墨烯层可以通过表面的所述第一活性官能团锚定相邻的功能层，从而形成平整、牢固的膜层。具体的，
当发光二极管为量子点发光二极管器件，且所述石墨烯层为设置在所述量子点发光层与所述底电极之间的石墨烯像素阵列时，一方面，通过所述石墨烯像素阵列表面的活性官能团，可以将所述量子点发光层中的量子点紧密地锚定在所述石墨烯像素阵列表面，从而形成致密均匀的量子点发光层，进而防止其在后续功能层的沉积过程中被溶剂溶解或冲走，提高了量子点发光层的成膜均匀性。另一方面，所述石墨烯像素阵列能够提供印刷位点（即覆盖有功能化石墨烯的区域能锚定量子点，而未覆盖功能化石墨烯区域的量子点在后续溶剂的冲洗下不能保留），从而能够代替目前常用的复杂且厚度较大的打印凹槽。此外，采用所述石墨烯像素阵列作为印刷位点，像素点的数量、距离等能够通过调节石墨烯层的图案灵活调节，提高了打印的灵活性和打印效率，且适于制备更轻薄的显示面板。
当所述石墨烯层为层叠结合在所述底电极上的图案化石墨烯层，且所述第一活性官能团修饰在所述石墨烯层朝向所述发光层的表面时，一方面，所述图案化石墨烯层能够为印刷型薄膜发光二极管提供打印位点，有利于各功能层的沉积。另一方面，所述石墨烯底电极可以直接作为印刷型薄膜发光二极管的导电电极，而在此基础上，形成的所述图案化石墨烯层可以作为空穴传输层。由于所述图案化石墨烯层含有丰富的活性官能团，所述活性官能团可以有效锚定进一步沉积的发光材料，从而形成均匀的发光层。而未覆盖所述图案化石墨烯层的区域由于不能锚定发光材料，在后续功能层的沉积过程中，可以通过溶剂清洗等途径能够轻松除去，最终有利于得到高分辨、高效率和高均匀性的印刷型薄膜发光二极管。
本发明提供的发光二极管器件的制备方法，通过将石墨烯像素阵列转印到底电极上，然后在所述石墨烯像素阵列修饰有活性官能团的表面沉积量子点，使得所述量子点能够通过所述活性官能团有效锚定在所述石墨烯像素阵列上，形成致密均匀的量子点发光层，提高了成膜均匀性。同时，采用所述石墨烯像素阵列作为印刷位点，可以简化发光二极管器件的制备工艺。且所述石墨烯像素阵列区域之外，由于偏离位点沉积的量子点能够通过清洗去除，从而提高了膜层的质量，进而有利于发光二极管器件性能的提高。本发明提供的发光二极管器件，具有优良的发光均匀性，较好的发光效率和器件稳定性，以及良好的结构设计灵活性。
 附图说明
图1是本发明实施例提供的发光二极管器件的制备流程示意图。
 本发明的实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例提供了一种发光二极管，包括相对设置的衬底和顶电极，所述衬底包括基板和设置在所述基板上的底电极，且所述底电极和所述顶电极之间设置有发光层，所述发光二极管还包括用于锚定相邻功能层的石墨烯层，且所述石墨烯层的表面修饰有第一活性官能团。
优选的，所述第一活性官能团为-OH、-COOH、-NH 2、-NH-、-NHCONH-、-SH、-CN、-SO 3H、-SOOH、-NO 2、-CONH 2、-CONH-、-COCl、-CO-、-O-、-COS-、-CH=N-、O=P(R) 2、-CHO、-Cl、-Br中的至少一种，但不限于此。优选的所述第一活性官能团，具有较好的反应活性，有利于与相邻的功能层如发光层、电子或空穴功能层材料键合连接，从而有效形成发光二极管的打印位点。特别的，当相邻的功能层为量子点发光层时，优选的所述第一活性官能团既可以与量子点表面的配体连接，也可以直接与量子点连接，双重锚定量子点，从而将所述量子点有效固定在所述石墨烯像素阵列表面。此外，优选的活性官能团能还能与量子点表面缺陷连接，同时起到钝化量子点表面缺陷的作用，进一步提高器件效率。进一步优选的，所述量子点发光二极管中的第一活性官能团为-OH、-COOH、-NH 2、-NH-、-SH、-CN、-SO 3H、-SOOH、-NO 2、-CONH 2、-CONH-、-COCl、-CO-、-CHO、-Cl、-Br中的至少一种。
作为一种实施方式，所述衬底为凹槽衬底，所述底电极为第一石墨烯电极，所述石墨烯层为层叠结合在所述底电极上的石墨烯层，所述石墨烯层为图案化石墨烯层，且所述第一活性官能团修饰在所述石墨烯层朝向所述发光层的表面，所述图案化石墨烯层通过所述第一活性官能团与背对所述底电极的相邻功能层结合。
本发明实施例中，在基板上设置的第一石墨烯电极和图案化石墨烯层共同形成图案化复合层，形成印刷型薄膜LED的像素阵列。其中，所述第一石墨烯电极可以作为导电电极，所述图案化石墨烯层作为空穴传输层，在此基础上沉积发光层时，由于所述第二图案化石墨烯层在朝向所述发光层的表面修饰有活性官能团，因此，可以有效锚定发光层材料（未覆盖所述第二图案化石墨烯层的区域由于不能发光材料，在后续功能层的沉积过程中，可以通过溶剂清洗等途径能够轻松除去），有利于提高发光层的成膜均匀性，进而提高发光二极管特别是印刷型薄膜发光二极管的性能。
本发明实施例中，所述第一石墨烯电极可以为整层石墨烯层，也可以形成图案化。当所述第一石墨烯电极为图案化的第一石墨烯电极时，所述第一石墨烯电极的图案与所述图案化石墨烯层的图案一致，两者实现完全重叠。
本发明实施例中，所述第一石墨烯电极为单层石墨烯或多层石墨烯，优选为单层石墨烯。本发明实施例中，所述图案化石墨烯层为单层石墨烯或多层石墨烯。
优选的，所述图案化石墨烯层的功函数范围为4.8eV~5.2eV，赋予所述图案化石墨烯层优良的空穴传输性能，从而匹配不同的量子点发光材料，以更好实现能带匹配，提高其性能。本发明实施例可以通过调节石墨烯的氧化程度、表面官能团种类、掺杂离子类型等途径，调节其禁带宽度，从而调节其空穴传输能力。
作为另一种实施方式，所述发光二极管为量子点发光二极管，所述发光层为量子点发光层，所述石墨烯层为设置在所述量子点发光层与所述底电极之间的石墨烯像素阵列，且所述量子点发光层通过所述第一活性官能团与所述石墨烯像素阵列结合。
本发明中，量子点发光二极管可以为正型量子点发光二极管，也可以为反型量子点发光二极管。作为一种实施情形，所述量子点发光二极管为正型量子点发光二极管，即所述底电极为阳极，所述顶电极为阴极。进一步的，所述阳极和所述量子点发光层之间设置有空穴注入层和/或空穴传输层，所述阴极和所述量子点发光层之间设置有电子注入层和/或电子传输层。
作为另一种实施情形，所述量子点发光二极管为反型量子点发光二极管，即所述底电极为阴极，所述顶电极为阳极。进一步的，所述阴极和所述量子点发光层之间设置有电子注入层和/或电子传输层，所述阳极和所述量子点发光层之间设置有空穴注入层和/或空穴传输层。
上述两种实施情形中，具体的，所述石墨烯像素阵列表面修饰有所述第一活性官能团，且所述第一活性官能团修饰在所述石墨烯像素阵列背对所述底电极的表面，以便实现与量子点发光层的结合。本发明实施例中，所述石墨烯像素阵列的图案没有严格的限制，可以设计成具有任意大小、任意形状的阵列图案；且所述石墨烯像素阵列可中像素点的大小、像素点的形状、像素点之间的间隔、像素点组合可以灵活设计。
优选的，所述石墨烯像素阵列的厚度为1-150nm。若所述石墨烯像素阵列的厚度过薄，则第一活性官能团的量过少，无法充分实现量子点的锚定；若所述石墨烯像素阵列的厚度过厚，会造成激子复合困难，降低器件发光效率。进一步优选的，所述石墨烯像素阵列的厚度为5-50nm，从而在兼顾良好的发光效率，实现量子点发光层与所述石墨烯像素阵列的紧密结合。
在上述实施例的基础上，进一步优选的，在所述石墨烯像素阵列的阵列之间（即没有覆盖功能化石墨烯的区域）设置有疏水疏氧隔绝层。所述疏水疏氧绝缘层一方面能够在沉积量子点发光层及其他功能层时，发挥隔板的作用，将各像素点隔离，有利于提高各功能层的沉积质量。且与传统的隔板相比，所述疏水疏氧隔绝层的厚度可以非常薄，从而能够制备出超薄的印刷量子点发光二极管。另一方面，所述疏水疏氧隔绝层具有疏水疏氧特点，从而有效防止由于沉积偏离在非像素点区域残留量子点，同时提高量子点发光二极管的防水防氧性能，提高印刷量子点发光二极管的分辨率及使用寿命。
具体的，所述疏水疏氧隔绝层由疏水疏氧有机物和/或疏水疏氧无机物制成。进一步优选的，所述疏水疏氧有机物包括聚甲基丙烯酸甲酯、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、聚对苯二甲酸丁二醇酯、对苯二甲酸乙二醇酯、聚酰亚胺、丁腈橡胶、氯苯橡胶、聚乙烯醇、聚碳酸酯、聚醚醚酮、聚醚砜、聚芳基酸酯、聚芳酯、聚乙烯吡咯烷酮、有机硅中的至少一种，但不限于此。所述疏水疏氧无机物为二氧化硅、三氧化二铝、氧化锆、氧化镁中的至少一种，但不限于此。优选的疏水疏氧隔绝层材料，可以更好地实现上述性能。
进一步优选的，所述量子点发光二极管中，所述底电极为图案化的第二石墨烯电极。所述第二石墨烯电极的选择可与所述第一石墨烯电极相同。进一步的，所述第二石墨烯电极表面设置有疏水层，所述第二石墨烯电极背对所述基板的表面修饰有第二活性官能团，所述疏水层中的疏水材料与所述第二活性官能团键合连接，从而牢固结合所述第二石墨烯电极，形成图案化的疏水区域（即图案化复合层），所述图案化复合层围合形成像素阵列凹槽。本发明实施例提供的所述像素阵列凹槽内壁（没沉积疏水层的部分）和底部，没有进行疏水处理，因此，对打印墨水具有亲和性，有利于各功能层的沉积。而用于隔离像素阵列的图案化复合层，由于进行了表面疏水处理，印刷过程中墨水不能有效浸润、成膜，从而在印刷功能层时，可以防止串色，并有效提高了发光二极管的印刷性能，进而提高器件的发光均匀性和器件稳定性。此外，采用本发明实施例提供的LED衬底，能满足各种超薄刚性或柔性器件的要求，简化了工艺复杂程度，提高了薄膜发光二极管结构的可塑性。
具体的，本发明实施例中，所述第二石墨烯电极背对所述基板的表面修饰有第二活性官能团。所述第二活性官能团能够与所述疏水材料键合结合，从而将所述疏水层牢固结合在所述图案化石墨烯层；而所述第二石墨烯电极以外的其他区域，由于不具备含有第二表面活性官能团的石墨烯，不能结合疏水材料而不具备疏水性，可以保证各功能层的顺利打印。由此，提高了印刷用薄膜LED衬底的打印性能。本发明实施例中，所述第二石墨烯电极中的石墨烯没有严格限定，可以为单层石墨烯或多层石墨烯。优选的，所述第二活性官能团为-OH、-COOH、-NH 2、-NH-、-SH、-CN、-SO 3H、-SOOH、-NO 2、-CONH 2、-CONH-、-COCl、-CO-、-CHO、-Cl、-Br中的至少一种，但不限于此。优选的所述第二活性官能团，具有较好的反应活性，有利于与所述疏水材料的结合。
本发明实施例中，所述疏水材料为有机高分子化合物。优选的，所述有机高分子化合物为聚甲基丙烯酸甲酯、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯、聚酰亚胺、丁腈橡胶、氯苯橡胶、聚乙烯醇、聚碳酸酯、聚醚醚酮、聚醚砜、聚芳基酸酯、聚芳酯、聚乙烯吡咯烷酮、聚四氟乙烯、有机硅及其衍生物中的至少一种。优选的所述有机高分子化合物，不仅具有较好的疏水性能，能够形成图案化的疏水区域，而且，上述有机高分子化合物与所述第二活性官能团、特别是优选的第二活性官能团具有较好的反应活性，有利于疏水材料的固定和疏水区域的形成。
在上述实施方式的基础上，用于本发明实施例的基板可以为刚性基板或柔性基板。具体的，所述基板为刚性基板或柔性基板，其中，所述刚性基板包括玻璃、金属箔片；所述柔性衬底包括聚对苯二甲酸乙二醇酯、聚对苯二甲酸乙二醇酯、聚醚醚酮、聚苯乙烯、聚醚砜、聚碳酸酯、聚芳基酸酯、聚芳酯、聚酰亚胺、聚氯乙烯、聚乙烯、聚乙烯吡咯烷酮、纺织纤维。
所述阳极可以选择量子点发光二极管领域常规的阳极材料。作为一种实施情形，所述阳极为掺杂金属氧化物，所述掺杂金属氧化物包括但不限于铟掺杂氧化锡（ITO）、氟掺杂氧化锡（FTO）、锑掺杂氧化锡（ATO）、铝掺杂氧化锌（AZO）、镓掺杂氧化锌（GZO）、铟掺杂氧化锌（IZO）、镁掺杂氧化锌（MZO）、铝掺杂氧化镁（AMO）中的一种或多种。作为另一种实施情形，所述阳极为透明金属氧化物中含有金属夹层的复合电极，其中，所述透明金属氧化物可以为掺杂透明金属氧化物，也可以为非掺杂的透明金属氧化物。所述复合电极包括但不限于AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO 2/Ag/TiO 2、TiO 2/Al/TiO 2、ZnS/Ag/ZnS、ZnS/Al/ZnS、TiO 2/Ag/TiO 2、TiO 2/Al/TiO 2中的一种或多种。
所述空穴注入层选自具有空穴注入能力的有机材料。制备所述空穴注入层的空穴注入材料包括但不限于聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸（PEDOT:PSS）、酞菁铜（CuPc）、2,3,5,6-四氟-7,7',8,8'-四氰醌-二甲烷（F4-TCNQ）、2,3,6,7,10,11-六氰基-1,4,5,8,9,12-六氮杂苯并菲（HATCN）、掺杂或非掺杂过渡金属氧化物、掺杂或非掺杂金属硫系化合物中的一种或多种。其中，所述过渡金属氧化物包括但不限于MoO 3、VO 2、WO 3、CrO 3、CuO中的至少一种；所述金属硫系化合物包括但不限于MoS 2、MoSe 2、WS 2、WSe 2、CuS中的至少一种。
所述空穴传输层选自具有空穴传输能力的有机材料，包括但不限于聚(9,9-二辛基芴-CO-N-(4-丁基苯基)二苯胺)（TFB）、聚乙烯咔唑（PVK）、聚(N, N'双(4-丁基苯基)-N,N'-双(苯基)联苯胺)（poly-TPD）、聚(9,9-二辛基芴-共-双-N,N-苯基-1,4-苯二胺)（PFB）、4,4’,4’’-三(咔唑-9-基)三苯胺（TCTA）、4,4'-二(9-咔唑)联苯（CBP）、N,N’-二苯基-N,N’-二(3-甲基苯基)-1,1’-联苯-4,4’-二胺（TPD）、N,N’-二苯基-N,N’-（1-萘基）-1,1’-联苯-4,4’-二胺（NPB）、掺杂石墨烯、非掺杂石墨烯、C60中的至少一种。作为另一个实施例，所述空穴传输层4选自具有空穴传输能力的无机材料，包括但不限于掺杂或非掺杂的MoO 3、VO 2、WO 3、CrO 3、CuO、MoS 2、MoSe 2、WS 2、WSe 2、CuS中的至少一种。
所述量子点发光层由常规的量子点制成，所述量子点可以为II-VI族纳米晶、III-V族纳米晶、II-V族纳米晶、III-VI族纳米晶、IV-VI族纳米晶、I-III-VI族纳米晶、II-IV-VI族纳米晶或IV族单质中的一种或多种。具体的，所述II-VI纳米晶包括CdS、CdSe、CdTe、ZnS、ZnSe、ZnTe、HgS、HgSe、HgTe、PbS、PbSe、PbTe，但不限于此，还可以为其他二元、三元、四元的II-VI纳米晶；所述III-V族纳米晶包括GaP、GaAs、InP、InAs，但不限于此，还可以为其他二元、三元、四元的III-V化合物。
作为一种优选实施情形，所述量子点为掺杂或非掺杂的无机钙钛矿型半导体、和/或有机-无机杂化钙钛矿型半导体。具体地，所述无机钙钛矿型半导体的结构通式为AMX 3，其中，A为Cs +离子，M为二价金属阳离子，包括但不限于Pb 2+、Sn 2+、Cu 2+、Ni 2+、Cd 2+、Cr 2+、Mn 2+、Co 2+、Fe 2+、Ge 2+、Yb 2+、Eu 2+，X为卤素阴离子，包括但不限于Cl -、Br -、I -。所述有机-无机杂化钙钛矿型半导体的结构通式为BMX 3，其中，B为有机胺阳离子，包括但不限于CH 3(CH 2) n-2NH 3 +(n≥2)或NH 3(CH 2) nNH 3 2+(n≥2)。当n=2时，无机金属卤化物八面体MX 6 4-通过共顶的方式连接，金属阳离子M位于卤素八面体的体心，有机胺阳离子B填充在八面体间的空隙内，形成无限延伸的三维结构；当n＞2时，以共顶的方式连接的无机金属卤化物八面体MX 6 4-在二维方向延伸形成层状结构，层间插入有机胺阳离子双分子层（质子化单胺）或有机胺阳离子单分子层（质子化双胺），有机层与无机层相互交叠形成稳定的二维层状结构；M为二价金属阳离子，包括但不限于Pb 2+、Sn 2+、Cu 2+、Ni 2+、Cd 2+、Cr 2+、Mn 2+、Co 2+、Fe 2+、Ge 2+、Yb 2+、Eu 2+，X为卤素阴离子，包括但不限于Cl -、Br -、I -。
所述电子传输层选自具有电子传输性能的材料，优选为具有电子传输性能的金属氧化物，所述金属氧化物包括但不限于n型ZnO、TiO 2、SnO 2、Ta 2O 3、AlZnO、ZnSnO、InSnO、Alq 3、Ca、Ba、CsF、LiF、CsCO 3中的至少一种。
所述阴极为各种导电碳材料、导电金属氧化物材料、金属材料中的一种或多种。其中，所述导电碳材料包括但不限于掺杂或非掺杂碳纳米管、掺杂或非掺杂石墨烯、掺杂或非掺杂氧化石墨烯、C60、石墨、碳纤维、多空碳、或它们的混合物；所述导电金属氧化物材料包括但不限于ITO、FTO、ATO、AZO、或它们的混合物；所述金属材料包括但不限于Al、Ag、Cu、Mo、Au、或它们的合金。其中，所述金属材料中，其形态包括但不限于纳米球、纳米线、纳米棒、纳米锥、纳米空心球、或它们的混合物。具体优选地，所述的阴极为Ag、Al。
进一步优选的，本发明实施例所述发光二极管还包括界面修饰层，所述界面修饰层为电子阻挡层、空穴阻挡层、电极修饰层、隔离保护层中的至少一层。
所述发光二极管的封装方式可以为部分封装、全封装、或不封装，本发明实施例没有严格限制。
当然，所述发光二极管可以为部分封装发光二极管、全封装发光二极管或不封装发光二极管。
本发明实施例提供的量子点发光二极管可以通过下述方法制备获得。
以及，本发明实施例还提供了一种发光二极管的制备方法，所述发光二极管为量子点发光二极管，包括以下步骤：
S01.沉积石墨烯层，对所述石墨烯层进行图案化处理形成石墨烯像素阵列，对所述石墨烯像素阵列的至少一表面进行修饰处理，使所述石墨烯像素阵列表面修饰有第一活性官能团，得到石墨烯像素阵列；
S02.提供衬底，所述衬底包括基板和设置在所述基板上的底电极，将所述石墨烯像素阵列转印到所述底电极上，且使得所述石墨烯像素阵列背对所述底电极的表面修饰有所述第一活性官能团；
S03.在所述石墨烯像素阵列上依次沉积量子点发光层。
具体的，上述步骤S01中，沉积石墨烯层的方法没有明确限定，只要能够得到覆盖均匀的石墨烯层即可。对所述石墨烯层进行图案化处理形成石墨烯像素阵列，优选采用光刻方法，但不限于此。通过光刻将所述石墨烯层图案化，形成石墨烯像素阵列。所述石墨烯像素阵列的设计如前文所述，可以灵活设计，为了节约篇幅，此处不再赘述。
进一步的，对所述石墨烯像素阵列至少一表面进行修饰处理，使所述石墨烯像素阵列表面修饰有第一活性官能团，优选采用化学处理和/或物理处理强酸实现。通过化学处理和/或物理处理，在石墨烯像素阵列至少一表面进行表面修饰，引入大量的第一活性官能团。优选的，所述化学处理为酸处理、碱处理、电化学处理、光化学处理中的至少一种。优选的，所述物理处理为等离子体处理、紫外臭氧处理、激光处理、热处理中的至少一种。优选的，所述第一活性官能团选自-OH、-COOH、-NH 2、-NH-、-NHCONH-、-SH、-CN、-SO 3H、-SOOH、-NO 2、-CONH 2、-CONH-、-COCl、-CO-、-O-、-COS-、-CH=N-、O=P(R) 2、-CHO、-Cl、-Br中的至少一种。
上述步骤S02中，所述衬底为凹槽衬底，作为一个优选实施例，所述凹槽衬底的制备方法为：
S021.在基板上沉积石墨烯材料层；
在基板上沉积石墨烯层的方法，没有严格的限定，可以采用直接沉积或转印沉积的方式。本发明实施例所述石墨烯的选择没有严格的限定，可以采用单层石墨烯或多层石墨烯。
S022.对所述石墨烯材料层进行图案化处理得到图案化的石墨烯电极，对所述石墨烯电极背离所述基板的表面进行修饰处理，使所述石墨烯电极背离所述基板的表面修饰有第二活性官能团，得到表面修饰有第二活性官能团的石墨烯电极；
对所述石墨烯材料层进行图案化处理，可以采用物理方法实现，优选采用刻蚀方法实现。具体的，可以采用等离子体刻蚀或光刻蚀途径将所述述石墨烯材料层刻蚀出具有预设图案或像素点阵列的样式。通过刻蚀形成凹槽结构，刻蚀掉的区域对应形成像素阵列区域。
进一步的，对所述石墨烯电极背离所述基板的表面进行修饰处理，使所述石墨烯电极背离所述基板的表面修饰有第二活性官能团。采用化学处理和/或物理处理对所述石墨烯电极背离所述基板的表面进行修饰处理，使所述所述石墨烯电极表面修饰有第二活性官能团，得到表面修饰有第二活性官能团的石墨烯电极。具体的，所述化学处理为酸处理、碱处理、电化学处理、光化学处理中的至少一种；所述物理处理为等离子体处理、紫外臭氧处理、激光处理、热处理中的至少一种。作为一个具体优选实施例，采用强酸将图案化的石墨烯表面活化，引入丰富的官能团，得到图案化的氧化石墨烯。进行修饰处理形成的所述活性官能团，其选择如前文所述，为了节约篇幅，此处不再赘述。
S023.在所述石墨烯电极表面沉积疏水材料，得到疏水层。
在所述石墨烯电极表面沉积疏水材料，所述疏水材料通过键合所述第二活性官能团，紧密连接在所述图案化石墨烯电极表面形成疏水层，从而使得图案化区域具有疏水性，印刷墨水不能有效浸润和成膜，由此也就形成了可有效印刷成膜的像素阵列凹槽。
作为另一个优选实施例，所述衬底为凹槽衬底，所述凹槽衬底的制备方法为：
S021.分别在两份基板上沉积石墨烯底电极和石墨烯层；
所述基板的选择没有严格的选择，具体参见上文。在所述基板上分别沉积石墨烯底电极和石墨烯层的方法，没有严格的限定。
S022.将所述石墨烯层进行表面修饰处理，使所述石墨烯层表面修饰有第一活性官能团，将所述石墨烯层转印到所述石墨烯底电极表面，且使得所述石墨烯层背对所述底电极的表面修饰有所述第一活性官能团；
将所述石墨烯层进行表面修饰处理，在所述石墨烯层表面形成氧化石墨烯，得到表面修饰后的石墨烯层，即使得所述石墨烯层表面修饰有第一活性官能团。具体的，可以采用化学处理和/或物理处理对所述石墨烯层进行表面修饰处理，使所述石墨烯层表面修饰有活性官能团。其中，所述化学处理为酸处理、碱处理、电化学处理、光化学处理中的至少一种；所述物理处理为等离子体处理、紫外臭氧处理、激光处理、热处理中的至少一种。作为一个具体优选实施例，采用强酸将所述石墨烯层进行表面活化，引入丰富的官能团。进行修饰处理形成的所述活性官能团，其选择如前文所述，为了节约篇幅，此处不再赘述。
进一步的，通过转印方法将表面修饰后的石墨烯层转印到所述石墨烯底电极表面，形成复合石墨烯层。
S023.将所述第二石墨烯层进行图案化处理，形成图案化石墨烯层，得到凹槽衬底。
根据发光二极管的预设像素阵列，将所述复合石墨烯层进行图案化处理，得到图案化的石墨烯层底电极和图案化石墨烯层，构成图案化复合层。具体的，所述图案化处理可以采用物理方法实现，优选采用刻蚀方法实现。具体的，可以采用等离子体刻蚀或光刻蚀途径将所述复合石墨烯层刻蚀出具有印刷型薄膜发光二极管的预设像素阵列的样式。所述样式没有限制，可以是具有任意大小、任意形状的图案；所述预设像素阵列可以具有任意像素点大小、任意像素点形状、任意像素点间隔、任意像素点组合。
作为再一种优选实施例，所述衬底为凹槽衬底，所述凹槽衬底的制备方法为：
S021.分别在两份基板上沉积石墨烯底电极和石墨烯层；
所述基板的选择没有严格的选择，具体参见上文。在所述基板上分别沉积石墨烯底电极和石墨烯层的方法，没有严格的限定。
S022.将所述石墨烯底电极、石墨烯层分别进行图案化处理后，对所述石墨烯层进行表面修饰处理，使所述石墨烯层表面修饰有第一活性官能团，将所述石墨烯层转印到所述石墨烯底电极表面，且使得所述石墨烯层背对所述底电极的表面修饰有所述第一活性官能团，得到凹槽衬底。
进一步的，将所述石墨烯像素阵列转印到所述底电极上，且使得修饰处理的表面背对所述底电极，从而有利于实现量子点发光层与所述功石墨烯像素阵列的紧密结合。
上述步骤S03中，在所述石墨烯像素阵列上沉积量子点发光层，所述量子点发光层中的量子点通过所述活性官能团与功能化石墨烯像素紧密结合。
本发明实施例中，作为一种实施方式，所述底电极为阳极，所述顶电极为阴极。作为另一种实施方式，所述底电极为阴极，所述顶电极为阳极。优选的，在所述石墨烯像素阵列和所述阳极之间设置有所述的空穴注入层和/或空穴传输层，在所述石墨烯像素阵列和所述量子点发光层之间设置有电子传输层。空穴注入层、空穴传输层、量子点发光层、电子传输层的沉积方法优选为印刷法，具体包括但不限于喷墨打印法、滚涂法、转印法、刮涂法、狭缝式涂布法、条状涂布法，进一步优选的，所述沉积方法为喷墨打印法。所述底电极、顶电极的沉积可以采用化学法或物理法实现，其中，所述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；所述物理法包括但不限于物理镀膜法或溶液加工法，其中，溶液加工法包括但不限于旋涂法、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、条状涂布法；物理镀膜法包括但不限于热蒸发镀膜法、电子束蒸发镀膜法、磁控溅射法、多弧离子镀膜法、物理气相沉积法、原子层沉积法、脉冲激光沉积法中的一种或多种。
下面，结合具体实施例进行说明。
实施例1
结合图1，一种正型印刷量子点发光二极管的制备方法，包括以下步骤：
S11.采用CVD法在铜片上制备出一层厚度为20nm的石墨烯层，将所述石墨烯层转移到硅片上，通过光刻方法将石墨烯层刻蚀成具有规整排布的石墨烯像素阵列4’，采用浓硫酸将该石墨烯像素阵列4’表面的石墨烯进行活化，使其表面带有大量活性官能团，得到石墨烯像素阵列4；
S12.在ITO阳极1上依次打印PEDOT空穴注入层2、TFB空穴传输层3，然后通过转印方法将石墨烯像素阵列4转移到TFB空穴传输层3上，且所述石墨烯像素阵列4带有大量活性官能团的表面背对所述空穴传输层3；
S13.采用打印方法在所述石墨烯像素阵列4上依次打印CdSe/ZnS量子点发光层5、ZnO电子传输层6，最后蒸镀Al阴极7，得到正型印刷量子点发光二极管。
实施例2
一种反型印刷量子点发光二极管的制备方法，包括以下步骤：
S21.采用CVD法在铜片上制备出一层厚度为20nm的石墨烯层，将所述石墨烯层转移到硅片上，通过光刻方法将石墨烯层刻蚀成具有规整排布的石墨烯像素阵列，采用浓硫酸将该石墨烯像素阵列表面的石墨烯进行活化，使其表面带有大量活性官能团，得到石墨烯像素阵列；
S22.在Al阴极上依次打印ZnO电子传输层，然后通过转印方法将石墨烯像素阵列转移到ZnO电子传输层上，且所述石墨烯像素阵列带有大量活性官能团的表面背对所述ZnO电子传输层；
S23.采用打印方法在所述石墨烯像素阵列上依次打印CdSe/ZnS量子点发光层、TFB空穴传输层、PEDOT空穴注入层，最后蒸镀ITO阳极，得到反型印刷量子点发光二极管。
实施例3
一种印刷型量子点发光二极管的制备方法，包括以下步骤：
S31.制备印刷用量子点发光二极管衬底，包括：
S31.分别在两份基板上沉积石墨烯底电极和石墨烯层；
S32.利用浓硫酸对所述石墨烯层进行表面修饰处理，引入活性官能团；将表面修饰处理后的所述石墨烯层转印到所述石墨烯底电极表面，形成复合石墨烯层；
S33.等离子体刻蚀所述复合石墨烯层，形成图案化复合层，得到印刷用量子点发光二极管衬底。
S32.在所述印刷用量子点发光二极管衬底中的图案化复合层上依次打印CdSe/ZnS量子点发光层、ZnO电子传输层，并沉积Al阴极，得到印刷型量子点发光二极管。
实施例4
一种印刷型有机发光二极管的制备方法，包括以下步骤：
S41.制备印刷用有机发光二极管衬底，包括
S411.采用CVD法在两份基板上沉积石墨烯底电极和石墨烯层；
S412.利用浓硫酸对所述石墨烯层进行表面修饰处理，引入活性官能团；将表面修饰处理后的所述石墨烯层转印到所述石墨烯底电极表面，形成复合石墨烯层；
S413.等离子体刻蚀所述复合石墨烯层，形成图案化复合层，得到印刷用有机发光二极管衬底。
S42.在所述印刷用OLED衬底中的凹槽区域依次打印发光层/电子传输层，并沉积Al阴极，得到印刷型有机发光二极管。
实施例5
一种印刷型量子点发光二极管器件的制备方法，包括以下步骤：
S51.制备印刷用量子点发光二极管衬底，包括
S511.在玻璃衬底上沉积一层石墨烯材料层，利用等离子体刻蚀法将石墨烯材料层刻蚀形成图案化，使被刻蚀掉的区域为具有规整像素点阵列的凹槽，得到图案化的石墨烯电极；
S512.利用浓硫酸将图案化的石墨烯电极表面活化，引入活性官能团，得到图案化的石墨烯电极；在该图案化石墨烯电极表面形成聚甲基丙烯酸甲酯层，得到印刷用量子点发光二极管衬底。其中，未覆盖石墨烯的区域形成像素阵列凹槽。
S52.在所述印刷用量子点发光二极管衬底中的凹槽区域依次沉积ITO阳极，打印PEDOT空穴注入层、TFB空穴传输层、CdSe/ZnS量子点发光层、ZnO电子传输层，蒸镀Al阴极，得到印刷量子点发光二极管。
实施例6
一种印刷型有机发光二极管的制备方法，包括以下步骤：
S61.制备印刷用有机发光二极管衬底，包括
S611.在玻璃衬底上沉积一层石墨烯材料层，利用等离子体刻蚀法将石墨烯层刻蚀形成图案化，使被刻蚀掉的区域为具有规整像素点阵列的凹槽，得到图案化的石墨烯电极；
S612.利用浓硫酸将图案化的石墨烯电极表面活化，引入活性官能团，得到图案化的石墨烯电极；在该图案化的石墨烯电极表面形成聚甲基丙烯酸甲酯层，得到印刷用有机发光二极管衬底。其中，未覆盖石墨烯的区域形成像素阵列凹槽。
S62.在所述印刷用有机发光二极管衬底中的凹槽区域依次沉积ITO阳极，打印PEDOT:PSS空穴注入层、NPB空穴传输层、Alq3发光层/电子传输层，蒸镀Al阴极，得到印刷有机发光二极管。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (20)

  1. 一种发光二极管，包括相对设置的衬底和顶电极，所述衬底包括基板和设置在所述基板上的底电极，且所述底电极和所述顶电极之间设置有发光层，其特征在于，所述发光二极管还包括用于锚定相邻功能层的石墨烯层，且所述石墨烯层的表面修饰有第一活性官能团；
    其中，所述衬底为凹槽衬底，所述底电极为第一石墨烯电极，所述石墨烯层为层叠结合在所述底电极上的石墨烯层，所述石墨烯层为图案化石墨烯层，且所述第一活性官能团修饰在所述石墨烯层朝向所述发光层的表面，所述图案化石墨烯层通过所述第一活性官能团与背对所述底电极的相邻功能层结合；
    或
    所述发光二极管为量子点发光二极管，所述发光层为量子点发光层，所述石墨烯层为设置在所述量子点发光层与所述底电极之间的石墨烯像素阵列，且所述量子点发光层通过所述第一活性官能团与所述石墨烯像素阵列结合。
  2. 如权利要求1所述的发光二极管，其特征在于，所述第一活性官能团为-OH、-COOH、-NH 2、-NH-、-NHCONH-、-SH、-CN、-SO 3H、-SOOH、-NO 2、-CONH 2、-CONH-、-COCl、-CO-、-O-、-COS-、-CH=N-、O=P(R) 2、-CHO、-Cl、-Br中的至少一种。
  3. 如权利要求1或2所述的发光二极管，其特征在于，所述凹槽衬底中，所述第一石墨烯电极为图案化的石墨烯电极，且所述第一石墨烯电极的图案与所述图案化石墨烯层的图案一致。
  4. 如权利要求1或2所述的发光二极管，其特征在于，所述凹槽衬底中，所述第一石墨烯电极为单层石墨烯或多层石墨烯；和/或
    所述图案化石墨烯层为单层石墨烯或多层石墨烯。
  5. 如权利要求1或2所述的发光二极管，其特征在于，所述凹槽衬底中，所述图案化石墨烯层的功函数范围为4.8eV~5.2eV。
  6. 如权利要求1或2所述的发光二极管，其特征在于，所述量子点发光二极管中，所述石墨烯像素阵列的厚度为1-150nm。
  7. 如权利要求1或2所述的发光二极管，其特征在于，所述量子点发光二极管中，在所述石墨烯像素阵列的阵列之间设置有疏水疏氧隔绝层。
  8. 如权利要求7所述的量子点发光二极管，其特征在于，所述疏水疏氧隔绝层由疏水疏氧有机物和/或疏水疏氧无机物制成。
  9. 如权利要求8所述的量子点发光二极管，其特征在于，所述疏水疏氧有机物为聚甲基丙烯酸甲酯、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、聚对苯二甲酸丁二醇酯、对苯二甲酸乙二醇酯、聚酰亚胺、丁腈橡胶、氯苯橡胶、聚乙烯醇、聚碳酸酯、聚醚醚酮、聚醚砜、聚芳基酸酯、聚芳酯、聚乙烯吡咯烷酮、有机硅中的至少一种；和/或
    所述疏水疏氧无机物为二氧化硅、三氧化二铝、氧化锆、氧化镁中的至少一种。
  10. 如权利要求1或2所述的发光二极管，其特征在于，所述量子点发光二极管中，所述底电极为阳极，所述顶电极为阴极，且所述阳极和所述量子点发光层之间设置有空穴注入层和/或空穴传输层，所述阴极和所述量子点发光层之间设置有电子注入层和/或电子传输层。
  11. 如权利要求1或2所述的发光二极管，其特征在于，所述量子点发光二极管中，所述底电极为阴极，所述顶电极为阳极，且所述阴极和所述量子点发光层之间设置有电子注入层和/或电子传输层，所述阳极和所述量子点发光层之间设置有空穴注入层和/或空穴传输层。
  12. 如权利要求1或2所述的发光二极管，其特征在于，所述量子点发光二极管中，所述底电极为图案化的第二石墨烯电极，且所述第二石墨烯电极表面设置有疏水层，所述第二石墨烯电极背对所述基板的表面修饰有第二活性官能团，所述疏水层中的疏水材料与所述第二活性官能团键合连接。
  13. 如权利要求12所述的发光二极管，其特征在于，所述疏水材料为有机高分子化合物。
  14. 如权利要求13所述的发光二极管，其特征在于，所述有机高分子化合物为聚甲基丙烯酸甲酯、聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯、聚酰亚胺、丁腈橡胶、氯苯橡胶、聚乙烯醇、聚碳酸酯、聚醚醚酮、聚醚砜、聚芳基酸酯、聚芳酯、聚乙烯吡咯烷酮、聚四氟乙烯、有机硅及其衍生物中的至少一种。
  15. 如权利要求14所述的发光二极管，其特征在于，所述第二活性官能团为-OH、-COOH、-NH 2、-NH-、-SH、-CN、-SO 3H、-SOOH、-NO 2、-CONH 2、-CONH-、-COCl、-CO-、-CHO、-Cl、-Br中的至少一种。
  16. 一种发光二极管的制备方法，其特征在于，所述发光二极管为量子点发光二极管，包括以下步骤：
    沉积石墨烯层，对所述石墨烯层进行图案化处理形成石墨烯像素阵列，对所述石墨烯像素阵列的至少一表面进行修饰处理，使所述石墨烯像素阵列表面修饰有第一活性官能团，得到石墨烯像素阵列；
    提供衬底，所述衬底包括基板和设置在所述基板上的底电极，将所述石墨烯像素阵列转印到所述底电极上，且使得所述石墨烯像素阵列背对所述底电极的表面修饰有所述第一活性官能团；
    在所述石墨烯像素阵列上依次沉积量子点发光层。
  17. 如权利要求16所述发光二极管的制备方法，其特征在于，采用化学处理和/或物理处理对所述石墨烯像素阵列的表面进行修饰处理，所述第一活性官能团选自-OH、-COOH、-NH 2、-NH-、-NHCONH-、-SH、-CN、-SO 3H、-SOOH、-NO 2、-CONH 2、-CONH-、-COCl、-CO-、-O-、-COS-、-CH=N-、O=P(R) 2、-CHO、-Cl、-Br中的至少一种。
  18. 如权利要求16所述发光二极管的制备方法，其特征在于，所述衬底为凹槽衬底，所述凹槽衬底的制备方法为：
    在基板上沉积石墨烯材料层；
    对所述石墨烯材料层进行图案化处理得到图案化的石墨烯电极，对所述石墨烯电极背离所述基板的表面进行修饰处理，使所述石墨烯电极背离所述基板的表面修饰有第二活性官能团，得到表面修饰有第二活性官能团的石墨烯电极；
    在所述石墨烯电极表面沉积疏水材料，得到疏水层。
  19. 如权利要求16所述发光二极管的制备方法，其特征在于，所述衬底为凹槽衬底，所述凹槽衬底的制备方法为：
    分别在两份基板上沉积石墨烯底电极和石墨烯层；
    将所述石墨烯层进行表面修饰处理，使所述石墨烯层表面修饰有第一活性官能团，将所述石墨烯层转印到所述石墨烯底电极表面，且使得所述石墨烯层背对所述底电极的表面修饰有所述第一活性官能团；
    将所述第二石墨烯层进行图案化处理，形成图案化石墨烯层，得到凹槽衬底。
  20. 如权利要求16所述发光二极管的制备方法，其特征在于，所述衬底为凹槽衬底，所述凹槽衬底的制备方法为：
    分别在两份基板上沉积石墨烯底电极和石墨烯层；
    将所述石墨烯底电极、石墨烯层分别进行图案化处理后，对所述石墨烯层进行表面修饰处理，使所述石墨烯层表面修饰有第一活性官能团，将所述石墨烯层转印到所述石墨烯底电极表面，且使得所述石墨烯层背对所述底电极的表面修饰有所述第一活性官能团，得到凹槽衬底。
PCT/CN2018/079467 2017-07-11 2018-03-19 发光二极管及其制备方法 WO2019010997A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710561444.6 2017-07-11
CN201710561444.6A CN109244252B (zh) 2017-07-11 2017-07-11 Qled器件及其制备方法

Publications (1)

Publication Number Publication Date
WO2019010997A1 true WO2019010997A1 (zh) 2019-01-17

Family

ID=65001123

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/079467 WO2019010997A1 (zh) 2017-07-11 2018-03-19 发光二极管及其制备方法

Country Status (2)

Country Link
CN (1) CN109244252B (zh)
WO (1) WO2019010997A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111943270B (zh) * 2020-08-21 2023-04-25 南京工程学院 一种用于制造二硫化钼量子点阵列的设备与工艺方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103441221A (zh) * 2013-09-16 2013-12-11 东南大学 基于石墨烯的柔性量子点发光二极管器件及其制备方法
CN103474425A (zh) * 2013-08-14 2013-12-25 中国科学院长春光学精密机械与物理研究所 高发光均匀性的微型柔性led面阵器件及制备方法
US20140087501A1 (en) * 2012-09-25 2014-03-27 International Business Machines Corporation Doped graphene transparent conductive electrode
CN104091892A (zh) * 2014-06-13 2014-10-08 重庆绿色智能技术研究院 一种基于石墨烯电极的有机半导体光电器件
CN105489767A (zh) * 2015-12-23 2016-04-13 中国科学院重庆绿色智能技术研究院 基于石墨烯/聚合物电极的柔性钙钛矿太阳能电池及制备
CN105957939A (zh) * 2016-05-28 2016-09-21 江苏积汇新能源科技有限公司 基于柔性石墨烯电极的垂直结构led加工方法
WO2016153228A1 (ko) * 2015-03-23 2016-09-29 재단법인 나노기반소프트일렉트로닉스연구단 그래핀 적층체 및 그의 제조방법

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120067158A (ko) * 2010-12-15 2012-06-25 삼성엘이디 주식회사 양자점 발광 소자
KR101462901B1 (ko) * 2012-11-29 2014-11-20 성균관대학교산학협력단 그래핀 양자점을 이용한 발광 소자 및 이를 포함하는 유기 발광 소자
CN105399080B (zh) * 2015-10-15 2018-06-29 南京工业大学 一种制备石墨烯-量子点复合材料的方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140087501A1 (en) * 2012-09-25 2014-03-27 International Business Machines Corporation Doped graphene transparent conductive electrode
CN103474425A (zh) * 2013-08-14 2013-12-25 中国科学院长春光学精密机械与物理研究所 高发光均匀性的微型柔性led面阵器件及制备方法
CN103441221A (zh) * 2013-09-16 2013-12-11 东南大学 基于石墨烯的柔性量子点发光二极管器件及其制备方法
CN104091892A (zh) * 2014-06-13 2014-10-08 重庆绿色智能技术研究院 一种基于石墨烯电极的有机半导体光电器件
WO2016153228A1 (ko) * 2015-03-23 2016-09-29 재단법인 나노기반소프트일렉트로닉스연구단 그래핀 적층체 및 그의 제조방법
CN105489767A (zh) * 2015-12-23 2016-04-13 中国科学院重庆绿色智能技术研究院 基于石墨烯/聚合物电极的柔性钙钛矿太阳能电池及制备
CN105957939A (zh) * 2016-05-28 2016-09-21 江苏积汇新能源科技有限公司 基于柔性石墨烯电极的垂直结构led加工方法

Also Published As

Publication number Publication date
CN109244252A (zh) 2019-01-18
CN109244252B (zh) 2020-11-10

Similar Documents

Publication Publication Date Title
WO2018113334A1 (zh) 量子点发光层与器件及制备方法、发光模组与显示装置
CN106601922B (zh) 一种量子点显示面板及其制作方法
CN108807720B (zh) 功能化阴极、qled及制备方法、发光模组与显示装置
CN110718637B (zh) 一种量子点发光二极管及其制备方法
CN109326727B (zh) 一种qled器件及其制备方法
CN109216566B (zh) 复合发光层、qled器件及其制备方法
US11183657B2 (en) Quantum dot light emitting diode and preparation method thereof
CN109216567B (zh) 复合发光层、qled器件及其制备方法
WO2018166094A1 (zh) 一种柔性显示器件及其制备方法
CN109390483B (zh) 一种显示设备及其制备方法
CN109427939B (zh) 一种qled器件及其制备方法
CN109285947B (zh) 印刷用led薄膜led衬底、led薄膜led器件及其制备方法
CN109285926B (zh) 印刷用薄膜led衬底、印刷型薄膜led器件及其制备方法
WO2019010997A1 (zh) 发光二极管及其制备方法
CN110739408B (zh) 量子点发光二极管及其制备方法
CN109935670B (zh) 表面配体、量子点薄膜、qled器件及其制备方法
WO2022143566A1 (zh) 发光器件及其制备方法
CN111384303B (zh) 一种膜层的制备方法与量子点发光二极管
CN109390493B (zh) 一种显示设备及其制备方法
CN109994650B (zh) 一种薄膜及其制备方法、应用
EP3796407A1 (en) Method for manufacturing element
CN109390492B (zh) 一种显示设备及其制备方法
CN111244305A (zh) 发光器件、显示装置及显示装置的制造方法
CN113130776B (zh) 一种量子点发光二极管及其制备方法
CN116940146A (zh) 一种发光器件及其制备方法、显示装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18831470

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18831470

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 29-07-2020)

122 Ep: pct application non-entry in european phase

Ref document number: 18831470

Country of ref document: EP

Kind code of ref document: A1