CN118284076A - Light-emitting device, preparation method thereof and display device - Google Patents
Light-emitting device, preparation method thereof and display device Download PDFInfo
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- CN118284076A CN118284076A CN202211734204.9A CN202211734204A CN118284076A CN 118284076 A CN118284076 A CN 118284076A CN 202211734204 A CN202211734204 A CN 202211734204A CN 118284076 A CN118284076 A CN 118284076A
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Abstract
The invention provides a light-emitting device, a preparation method thereof and a display device, and relates to the technical field of display. The light emitting device includes: an anode and a cathode disposed opposite each other; the first light-emitting unit is arranged between the anode and the cathode and comprises an inorganic light-emitting layer; the second light-emitting unit is arranged between the first light-emitting unit and the cathode and comprises an organic light-emitting layer; the charge generation layer is arranged between the first light-emitting unit and the second light-emitting unit; and an interface modification layer arranged between the charge generation layer and the second light-emitting unit, wherein the material of the interface modification layer is selected from one or more of insulating materials and hole transport materials with HOMO energy level less than or equal to-5.8 eV. The carrier balance problem of the light emitting device provided by the invention is improved.
Description
Technical Field
The invention relates to the technical field of display, in particular to a light-emitting device, a preparation method thereof and a display device.
Background
The stacked structure in which light emitting units including light emitting layers are connected in series has advantages of high current efficiency and long operation life, and thus is widely used in the field of display technology. However, the current stacked devices have unbalanced carrier transport, resulting in lower device efficiency and more complex device structure, thus greatly limiting the development of stacked technology.
Disclosure of Invention
The present invention aims to provide a light emitting device with improved carrier balance.
Another object of the present invention is to provide a method of manufacturing a light emitting device.
It is still another object of the present invention to provide a display device.
The invention solves the technical problems by adopting the following technical scheme:
A light emitting device comprising:
An anode and a cathode disposed opposite each other;
The first light-emitting unit is arranged between the anode and the cathode and comprises an inorganic light-emitting layer;
The second light-emitting unit is arranged between the first light-emitting unit and the cathode and comprises an organic light-emitting layer;
the charge generation layer is arranged between the first light-emitting unit and the second light-emitting unit; and
The interface modification layer is arranged between the charge generation layer and the second light-emitting unit, and the material of the interface modification layer is selected from one or more of insulating materials and hole transport materials with HOMO energy levels smaller than or equal to-5.8 eV.
Optionally, in some embodiments of the invention, the hole transport material is selected from one or more of PVK, polyfluorene, CBP; and/or
The insulating material is one or more selected from polystyrene, polymethyl methacrylate, polyvinylpyrrolidone, polyacetylimide, polyethoxy imide, polyethylene and polyether ether ketone.
Alternatively, in some embodiments of the present invention, the hole transport material has a HOMO level of-8 eV to-5.8 eV; and/or
The thickness of the interface modification layer is 1-10 nm; and/or
The thickness of the organic light emitting layer is 30-100 nm.
Alternatively, in some embodiments of the present invention, the material of the organic light emitting layer is a copolymer.
Alternatively, in some embodiments of the present invention, the monomers of the copolymer include a first compound selected from one or more of an alkylfluorene, an alkoxybenzene, and a second compound selected from one or more of a2, 1, 3-benzothiadiazole, a2, 1, 3-benzoselenadiazole, and a pyridine.
Alternatively, in some embodiments of the invention, the alkylfluorene is selected from one or more of 2, 7-dibromo-9, 9-behenyl fluorene, 2, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-bis (dodecyl) fluorene; and/or
The alkoxybenzene is selected from one or more of 1, 3-didodecyloxy benzene and 5-bromo-1, 2, 3-tri (dodecyloxy) benzene; and/or
The mole percentage content of the first compound in the copolymer is 15-70%; and/or
The mole percentage of the second compound in the copolymer is 30-85%; and/or
The peak light-emitting wavelength of the organic light-emitting layer is 650-1200 nm; and/or
The peak emission wavelength of the inorganic light-emitting layer is 650-1200 nm.
Optionally, in some embodiments of the invention, the first light emitting unit further comprises a first hole functional layer disposed between the anode and the inorganic light emitting layer, the first hole functional layer comprising a first hole injection layer and/or a first hole transport layer;
the charge generation layer comprises an electron transport layer and a second hole injection layer which are stacked; the electron transport layer is disposed adjacent to the inorganic light emitting layer, and the second hole injection layer is disposed adjacent to the interface modification layer.
Optionally, in some embodiments of the invention, the material of the anode is selected from one or more of doped or undoped metal oxides, carbon silicon materials, metals, composite electrode materials; wherein the doped or undoped metal oxide is selected from one or more of ITO, FTO, ATO, IZO, ITZO, ICO, snO 2、In2O3、Cd:ZnO、Ga:SnO2, AZO, GZO, MZO, AMO; the carbon-silicon material is selected from one or more of silicon, graphite, carbon nano tube, graphene and carbon fiber; the metal is selected from one or more of Al, ag, cu, mo, au, ba, ca, mg; the composite electrode material is selected from one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS; and/or
The cathode material is selected from one or more of doped or undoped metal, carbon silicon material, doped or undoped metal oxide and composite electrode material; wherein the doped or undoped metal is selected from one or more of Al、Ag、Cu、Mo、Au、Ba、Ca、Mg、Pt、Ca:Al、LiF:Ca、LiF:Al、BaF2:Al、CsF:Al、CaCO3:Al、BaF2:Ca:Al、Au:Mg、Ag:Mg; the carbon-silicon material is selected from one or more of silicon, graphite, carbon nano tube, graphene and carbon fiber; the doped or undoped metal oxide is selected from one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO; the composite electrode material is selected from one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS; and/or
The materials of the first hole injection layer and the second hole injection layer are respectively and independently selected from poly (ethylenedioxythiophene): polystyrene sulfonate, poly [9, 9-dioctyl-fluorene-co-N- (4-butylphenyl) -diphenylamine ], polyarylamine, poly (N-vinylcarbazole), polyaniline, polythiophene, polypyrrole, N, N, N ', N' -tetrakis (4-methoxyphenyl) -benzidine, 4-bis [ N- (1-naphthyl) -N-phenyl-amino ] biphenyl, 4 '-tris [ phenyl (m-tolyl) amino ] triphenylamine, 4', one or more of 4 "-tris (N-carbazolyl) -triphenylamine, 1-bis [ (di-4-tolylamino) phenylcyclohexane, tetrafluoro-tetracyano-quinone dimethane doped 4,4',4" -tris (diphenylamino) triphenylamine, p-doped phthalocyanine, F4-TCNQ doped N, N' -diphenyl-N, N '-bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine, hexaazabenzophenanthrene-hexanenitrile; and/or
The material of the first hole transport layer is selected from one or more of arylamine, polyaniline, polyfluorene, polypyrrole, poly (p-phenylene vinylene) and its derivatives, copper phthalocyanine, aromatic tertiary amine or polynuclear aromatic tertiary amine, 4' -bis (p-carbazolyl) -1,1' -biphenyl compound, N ' -tetraarylbenzidine, PEDOT: PSS and its derivatives, poly (N-vinylcarbazole) and its derivatives, polymethacrylate and its derivatives, poly (9, 9-octylfluorene) and its derivatives, poly (spirofluorene) and its derivatives, N ' -bis (naphthalene-1-yl) -N, N ' -diphenyl benzidine, spironpb; and/or
The material of the electron transport layer is one or more selected from inorganic materials and organic materials; wherein the inorganic material is selected from one or more of doped or undoped oxides, doped or undoped semiconductor particles, and nitrides, the oxides are selected from one or more of TiO2、ZnO、ZrO2、SnO2、WO3、NiO、Ta2O3、HfO2、Al2O3、ZrSiO4、BaTiO3、BaZrO3、SrTiO3、MgTiO3、TiLiO、ZnMgO、ZnAlO、ZnMgLiO、ZnSnO、ZnLiO、InSnO, the semiconductor particles are selected from one or more of CdS, znSe, znS, the nitrides are selected from Si 3N4, and the doping elements of the oxides and the semiconductor particles are respectively and independently selected from one or more of Al, mg, in, li, ga, cd, cs, cu; the organic material is one or more selected from Alq3, almq3 and DVPBi, TAZ, OXD, PBD, BND, PV; and/or
The material of the inorganic luminescent layer comprises quantum dots, wherein the quantum dots are selected from one or more of single-structure quantum dots, core-shell structure quantum dots and doped or undoped inorganic perovskite type quantum dots; wherein the single-structure quantum dot is selected from one or more of II-VI compound, III-V compound, II-V compound, III-VI compound, IV-VI compound, I-III-VI compound, II-IV-VI compound and IV simple substance, the II-VI compound is selected from one or more of CdSe、CdS、CdTe、ZnSe、ZnS、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe、CdZnSTe, the III-V compound is selected from one or more of InP, inAs, gaP, gaAs, gaN, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP, inAlNP, and the IV-VI compound is selected from one or more of PbS, pbSe, pbTe; the I-III-VI compound is selected from one or more of CuInS 2、CuInSe2、AgInS2; the IV group simple substance is selected from one or more of silicon and germanium; the core of the quantum dot with the core-shell structure is selected from any one of quantum dots with single structures, and the shell material of the quantum dot with the core-shell structure is selected from one or more of CdS, cdTe, cdSe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znTe, znSeS, znS; the structural general formula of the inorganic perovskite type quantum dot is AMX 3, wherein A is Cs +, M is selected from one or more of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, and X is selected from one or more of Cl -、Br-、I-.
In addition, a method of manufacturing a light emitting device includes:
Sequentially stacking an anode, a first light-emitting unit, a charge generation layer, an interface modification layer, a second light-emitting unit and a cathode; or sequentially laminating a cathode, a second light-emitting unit, an interface modification layer, a charge generation layer, a first light-emitting unit and an anode;
The first light-emitting unit comprises an inorganic light-emitting layer, the second light-emitting unit comprises an organic light-emitting layer, and the interface modification layer is made of one or more of insulating materials and hole transport materials with HOMO energy levels smaller than or equal to-5.8 eV.
In addition, a display device comprises the light-emitting device or the light-emitting device prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects: the serial laminated device provided by the scheme comprises the interface modification layer arranged between the light-emitting unit and the charge generation layer, the interface modification layer can regulate and control hole injection of the light-emitting unit, carrier balance of the laminated device is regulated and controlled, and the device is simple in structure.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a light emitting diode according to embodiment 1 of the present invention.
Wherein the reference numerals are summarized as follows:
an anode 101; a first hole injection layer 102; a first hole transport layer 103; an inorganic light emitting layer 104; an electron transport layer 105; a second hole injection layer 106; an interface modification layer 107; an organic light emitting layer 108; and a cathode 109.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The technical scheme provided by the invention will be described in detail below. The following description of the embodiments is not intended to limit the preferred embodiments. In addition, in the description of the present invention, the term "comprising" means "including but not limited to". The terms "first," "second," "third," and the like are used merely as labels, and do not impose numerical requirements or on order of establishment. Various embodiments of the invention may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range.
The present invention provides a light emitting device including:
An anode and a cathode disposed opposite each other;
The first light-emitting unit is arranged between the anode and the cathode and comprises an inorganic light-emitting layer;
The second light-emitting unit is arranged between the first light-emitting unit and the cathode and comprises an organic light-emitting layer;
the charge generation layer is arranged between the first light-emitting unit and the second light-emitting unit; and
The interface modification layer is arranged between the charge generation layer and the second light-emitting unit, and the material of the interface modification layer is selected from one or more of insulating materials and hole transport materials with HOMO energy levels smaller than or equal to-5.8 eV.
Since the first light emitting unit includes an inorganic light emitting layer and the second light emitting unit includes an organic light emitting layer, the light emitting device is an inorganic-organic stacked device.
Further, the hole transport material is selected from one or more of PVK, polyfluorene and CBP; the insulating material is one or more selected from Polystyrene (PS), polymethyl methacrylate (PMMA), polyvinylpyrrolidone, polyacetyl imine, polyethoxy imide, polyethylene and polyether ether ketone.
In some embodiments, the hole transport material has a HOMO level of-8 eV to-5.8 eV. For example, -8eV, -7.5eV, -7eV, -6.5eV, -6eV, -5.8eV.
In some embodiments, the thickness of the interface modification layer is 1 to 10nm, e.g., 3nm, 5nm, 6nm, 8nm.
In some embodiments, the thickness of the organic light emitting layer is 30 to 100nm, and may be 35 to 50nm, 45 to 60nm, 50 to 90nm, 70 to 80nm.
In some embodiments, the material of the organic light emitting layer is a copolymer. The copolymer may be a copolymer having electron and hole transport capabilities. The copolymer is selected as the material of the organic light emitting layer, so that the efficiency of the device can be improved.
In some embodiments, the monomers of the copolymer include a first compound selected from one or more of alkyl fluorenes, alkoxy benzenes, and a second compound selected from one or more of 2,1, 3-benzothiadiazole (CAS: 273-13-2), 2,1, 3-benzoselenadiazole (CAS: 273-15-4), pyridine. Further, the alkylfluorene is selected from one or more of 2, 7-dibromo-9, 9-behenyl fluorene (CAS: 286438-45-7), 2, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-bis (dodecyl) fluorene (CAS: 749900-93-4); the alkoxybenzene is selected from one or more of 1, 3-didodecyloxy benzene (CAS: 41662-92-4) and 5-bromo-1, 2, 3-tri (dodecyloxy) benzene (CAS: 654065-52-8).
In some embodiments, the mole percent of the first compound in the copolymer is 15-70%, such as 20%, 33%, 40%, 50%, 62%, 68%; the second compound is present in the copolymer in a molar percentage of 30 to 85%, for example 35%, 40%, 48%, 55%, 71%, 80%.
In some embodiments, the peak emission wavelength of the organic light emitting layer is 650-1200 nm.
In some embodiments, the peak emission wavelength of the inorganic light-emitting layer is 650-1200 nm
The device type of the light emitting device provided by the invention is not limited to a double-layer device, a three-layer device, a multi-layer device, a top emitter device, a bottom emitter device, a double-sided emission device, a rigid device, a flexible device, and the like. The light emitting device may be one of a quantum dot light emitting diode (QLED), an Organic Light Emitting Diode (OLED), a sub-millimeter light emitting diode (Mini LED), and a Micro light emitting diode (Micro LED).
In some embodiments, the first light emitting unit further comprises a first hole functional layer disposed between the anode and the inorganic light emitting layer, the first hole functional layer comprising a first hole injection layer and/or a first hole transport layer;
the charge generation layer comprises an electron transport layer and a second hole injection layer which are stacked; the electron transport layer is disposed adjacent to the inorganic light emitting layer, and the second hole injection layer is disposed adjacent to the interface modification layer.
In some embodiments, a light emitting device includes an anode, a first hole injection layer, a first hole transport layer, an inorganic light emitting layer, an electron transport layer, a second hole injection layer, an interface modification layer, an organic light emitting layer, and a cathode in a stacked arrangement.
In some embodiments, the material of the anode may be selected from one or more of doped or undoped metal oxides, carbon silicon materials, metals, composite electrode materials; wherein the doped or undoped metal oxide is selected from one or more of ITO, FTO, ATO, IZO, ITZO, ICO, snO 2、In2O3、Cd:ZnO、Ga:SnO2, AZO, GZO, MZO, AMO; the carbon-silicon material is selected from one or more of silicon, graphite, carbon nano tube, graphene and carbon fiber; the metal is selected from one or more of Al, ag, cu, mo, au, ba, ca, mg; the composite electrode material is selected from one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS, i.e., the anode may be a composite electrode with metal sandwiched between doped or undoped metal oxides.
The material of the cathode can be selected from one or more of doped or undoped metal, carbon silicon material, doped or undoped metal oxide and composite electrode material; wherein the doped or undoped metal is selected from one or more of Al、Ag、Cu、Mo、Au、Ba、Ca、Mg、Pt、Ca:Al、LiF:Ca、LiF:Al、BaF2:Al、CsF:Al、CaCO3:Al、BaF2:Ca:Al、Au:Mg、Ag:Mg, and the doped metal electrode is an alloy electrode; the carbon-silicon material is selected from one or more of silicon, graphite, carbon nano tube, graphene and carbon fiber; the doped or undoped metal oxide is selected from one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO; the composite electrode material is selected from one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS, i.e. the cathode may be a composite electrode of AZO/Ag/AZO, AZO/Al/AZO, for example. The thickness of the cathode may be 80 to 500nm.
The materials of the first hole injection layer and the second hole injection layer are respectively and independently selected from poly (ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS), poly [9, 9-dioctyl-fluorene-co-N- (4-butylphenyl) -diphenylamine ] (TFB), polyarylamine, poly (N-vinylcarbazole) (PVK), polyaniline (Pan), polythiophene, polypyrrole (PPY), N, N, N ', N ' -tetra (4-methoxyphenyl) -benzidine (TPD), 4-bis [ N- (1-naphthyl) -N-phenyl-amino ] biphenyl (. Alpha. -NPD), 4',4 "-tris [ phenyl (m-tolyl) amino ] triphenylamine (m-MTDATA), 4',4" -tris (N-carbazolyl) -triphenylamine (TCTA), 1-bis [ (di-4-tolylamino) phenylcyclohexane (TAPC), 4',4 "-tris (diphenylamino) triphenylamine (TDATA) doped with tetrafluoro-tetracyano-quinone dimethane (F4-TCNQ), p-doped phthalocyanines (e.g., F4-TCNQ-doped zinc phthalocyanine)
(ZnPc)), F4-TCNQ doped N, N ' -diphenyl-N, N ' -bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine (α -NPD), hexaazabenzophenanthrene-hexanenitrile (HAT-CN). The thickness of the first hole injection layer and the second hole injection layer can be 10-50 nm independently.
The material of the first hole transport layer may be selected from arylamines such as 4,4' -N, N ' -dicarbazolyl-biphenyl (CBP), N ' -diphenyl-N, N ' -bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine (a-NPD), N ' -diphenyl-N, N ' -bis (3-methylphenyl) - (1, 1' -biphenyl) -4,4' -diamine (TPD), N ' -bis (3-methylphenyl) -N, N ' -bis (phenyl) -spiro (spiro-TPD), N, N ' -bis (4- (N, N ' -diphenyl-amino) phenyl) -N, N ' -diphenyl benzidine (DNTPD), 4' -tris (N-carbazolyl) -triphenylamine (TCTA), tris (3-methylphenyl-phenylamino) -triphenylamine (m-MTDATA), TAPC, poly [ (9, 9' -dioctylfluorene-2, 7-diyl) -co- (4, 4' - (N- (4-sec-butylphenyl) diphenylamine)) ] (TFB) and poly (4-butylphenyl-diphenylamine) (poly-TPD); polyaniline; polyfluorene; polypyrrole; poly (p) phenylenevinylenes and derivatives thereof, such as poly (phenylenevinylene) (PPV), poly [ 2-methoxy-5- (2-ethylhexyloxy) -1, 4-phenylenevinylene ] (MEH-PPV) and poly [ 2-methoxy-5- (3 ',7' -dimethyloctyloxy) -1, 4-phenylenevinylene ] (MOMO-PPV); copper phthalocyanine; aromatic tertiary amines or polynuclear aromatic tertiary amines; 4,4 '-bis (p-carbazolyl) -1,1' -biphenyl compounds; n, N' -tetraarylbenzidine; PEDOT PSS and its derivatives; poly (N-vinylcarbazole) (PVK) and derivatives thereof; polymethacrylate and derivatives thereof; poly (9, 9-octylfluorene) and derivatives thereof; poly (spirofluorene) and derivatives thereof; n, N '-bis (naphthalen-1-yl) -N, N' -diphenyl benzidine (NPB); spiro NPB; or a combination of the foregoing.
The material of the electron transport layer may be selected from one or more of inorganic materials, organic materials. Wherein the inorganic material may be selected from one or more of doped or undoped oxides, doped or undoped semiconductor particles, nitrides. Further, the oxide may be selected from, but not limited to TiO2、ZnO、ZrO2、SnO2、WO3、NiO、Ta2O3、HfO2、Al2O3、ZrSiO4、BaTiO3、BaZrO3、SrTiO3、MgTiO3、TiLiO、ZnMgO、ZnAlO、ZnMgLiO、ZnSnO、ZnLiO、InSnO; semiconductor particles may be selected from, but not limited to CdS, znSe, znS; the nitride may be Si 3N4; the doping elements of the oxide and semiconductor particles may be selected from, but are not limited to Al, mg, in, li, ga, cd, cs, cu, respectively. The organic material of the electron transport layer may be selected from one or more of an oxazole compound, an isoxazole compound, a triazole compound, an isothiazole compound, an oxadiazole compound, a thiadiazole compound, a perylene compound, and an aluminum complex, and further, may be selected from one or more of, but not limited to, alq3, almq3, DVPBi, TAZ, OXD, PBD, BND, PV. The material of the electron transport layer comprises one or more of ZnO, zn x1Mgy1O、Znx1Aly1O、Znx2Mgy2Liz2 O, wherein x1+y1=1 or x2+y2+z2=1. The thickness of the electron transport layer may be 20 to 60nm.
The material of the inorganic luminescent layer comprises quantum dots, wherein the quantum dots are selected from one or more of single-structure quantum dots, core-shell structure quantum dots and doped or undoped inorganic perovskite type quantum dots; wherein the single-structure quantum dot is selected from one or more of II-VI compound, III-V compound, II-V compound, III-VI compound, IV-VI compound, I-III-VI compound, II-IV-VI compound and IV simple substance, the II-VI compound is selected from one or more of CdSe、CdS、CdTe、ZnSe、ZnS、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe、CdZnSTe, the III-V compound is selected from one or more of InP, inAs, gaP, gaAs, gaN, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP, inAlNP, and the IV-VI compound is selected from one or more of PbS, pbSe, pbTe; the I-III-VI compound is selected from one or more of CuInS 2、CuInSe2、AgInS2; the IV group simple substance is selected from one or more of silicon and germanium; the core of the quantum dot with the core-shell structure is selected from any one of quantum dots with single structures, and the shell material of the quantum dot with the core-shell structure is selected from one or more of CdS, cdTe, cdSe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znTe, znSeS, znS; the structural general formula of the inorganic perovskite type quantum dot is AMX 3, wherein A is Cs +, M is selected from one or more of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2+、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, and X is selected from one or more of Cl -、Br-、I-. The peak luminescence wavelength of the material of the inorganic luminescent layer may be 650 to 1200nm, and the thickness of the inorganic luminescent layer may be 10 to 50nm.
In addition, the invention also provides a preparation method of the light-emitting device, which comprises the following steps:
Sequentially stacking an anode, a first light-emitting unit, a charge generation layer, an interface modification layer, a second light-emitting unit and a cathode; or sequentially laminating a cathode, a second light-emitting unit, an interface modification layer, a charge generation layer, a first light-emitting unit and an anode;
The first light-emitting unit comprises an inorganic light-emitting layer, the second light-emitting unit comprises an organic light-emitting layer, and the interface modification layer is made of one or more of insulating materials and hole transport materials with HOMO energy levels smaller than or equal to-5.8 eV.
It should be noted that, in the preparation method, reference to "forming another structural layer/unit on" a certain structural layer/unit is a broad concept, including "on" having a contact or adjacent relationship, and also including "above" having a spaced relationship, which may mean that the formed another structural layer/unit is adjacent to the certain structural layer/unit, and may also mean that a spacer layer/unit exists between the another structural layer/unit and the certain structural layer/unit.
The deposition/fabrication of the various structural layers of the light emitting device may be accomplished using techniques well known in the art, including using chemical or physical methods. The chemical method is, for example, chemical vapor deposition, continuous ion layer adsorption and reaction, anodic oxidation, electrolytic deposition, or coprecipitation. The physical method may be a physical plating method or a solution processing method. Specifically, the physical plating method is, for example, a thermal evaporation plating method, an electron beam evaporation plating method, a magnetron sputtering method, a multi-arc ion plating method, a physical vapor deposition method, an atomic layer deposition method, a pulse laser deposition method; examples of the solution processing method include spin coating, printing, inkjet printing, knife coating, printing, dip-coating, dipping, spraying, roll coating, casting, slit coating, and bar coating. Specific treatment methods and treatment conditions can be referred to as common methods in the art, and will not be described herein.
In addition, the invention also provides a display device comprising the light-emitting device or the light-emitting device prepared by the preparation method.
Example 1
The embodiment provides a light emitting diode, the structure of which is shown in fig. 1, and in addition, the embodiment also provides a preparation method of the light emitting diode, which includes:
s1, preparing a first hole injection layer 102 on an anode 101 made of ITO (indium tin oxide), wherein the material is polyaniline, and the thickness is 40nm;
S2, preparing a first hole transport layer 103 on the first hole injection layer 102, wherein the material is TFB, and the thickness is 25nm;
S3, preparing an infrared inorganic luminescent layer 104 on the first hole transport layer 103, wherein the inorganic luminescent layer 104 is made of PbS/CdS (peak luminescence wavelength is 900 nm) and has a thickness of 35nm;
S4, preparing an electron transport layer 105 on the inorganic luminescent layer 104, wherein the material is Zn 0.85Mg0.15 O, and the thickness is 40nm;
S5, preparing a second hole injection layer 106 on the electron transport layer 105, wherein the material is PEDOT PSS, and the thickness is 50nm;
s6, preparing an interface modification layer 107 on the second hole injection layer 106, wherein the material is PMMA, and the thickness is 5nm;
S7, preparing an organic light-emitting layer 108 on the interface modification layer 107, wherein the material of the organic light-emitting layer 108 is a copolymer of 2, 7-dibromo-9, 9-docosahexaenoic acid and 2,1, 3-benzothiadiazole (the peak light-emitting wavelength is 900 nm), and the thickness of the organic light-emitting layer 108 is 60nm;
s8, preparing a cathode 109 by a vacuum evaporation process, wherein the material is silver, and the thickness is 100nm.
Example 2
The light emitting diode and the preparation method thereof provided in this embodiment are basically the same as those in embodiment 1, except that: in step S7 of this embodiment, the material of the organic light emitting layer is a copolymer of 2, 7-dibromo-9, 9-docosane-yl fluorene and 2,1, 3-benzoselenadiazole.
Example 3
The light emitting diode and the preparation method thereof provided in this embodiment are basically the same as those in embodiment 1, except that: in step S6 of the present embodiment, the material of the interface modification layer is polyfluorene.
Example 4
The light emitting diode and the preparation method thereof provided in this embodiment are basically the same as those in embodiment 1, except that: in step S6 of the present embodiment, the material of the interface modification layer is polystyrene.
Comparative example 1
The light emitting diode and the manufacturing method thereof provided in this comparative example are substantially the same as those in example 1, except that: in step S7 of this comparative example, the material of the organic light emitting layer was MEH-PPV.
The devices provided in examples 1 to 4 and comparative example 1 were tested and the test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the light-emitting device provided by the invention has higher external quantum efficiency and good device performance.
The foregoing has outlined the detailed description of the embodiments of the present invention, and the detailed description of the principles and embodiments of the present invention is provided herein by way of example only to facilitate the understanding of the method and core concepts of the present invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present invention, the present description should not be construed as limiting the present invention.
Claims (10)
1. A light emitting device, comprising:
An anode and a cathode disposed opposite each other;
a first light emitting unit disposed between the anode and the cathode, the first light emitting unit including an inorganic light emitting layer;
A second light emitting unit disposed between the first light emitting unit and the cathode, the second light emitting unit including an organic light emitting layer;
a charge generation layer disposed between the first light emitting unit and the second light emitting unit; and
And the interface modification layer is arranged between the charge generation layer and the second light-emitting unit, and the material of the interface modification layer is one or more selected from insulating materials and hole transport materials with HOMO energy levels less than or equal to-5.8 eV.
2. The light-emitting device according to claim 1, wherein the hole transport material is one or more selected from PVK, polyfluorene, CBP; and/or
The insulating material is one or more selected from polystyrene, polymethyl methacrylate, polyvinylpyrrolidone, polyacetylimide, polyethoxy imide, polyethylene and polyether ether ketone.
3. The light-emitting device according to claim 1, wherein a HOMO level of the hole-transporting material is-8 eV to-5.8 eV; and/or
The thickness of the interface modification layer is 1-10 nm; and/or
The thickness of the organic light-emitting layer is 30-100 nm.
4. A light-emitting device according to any one of claims 1 to 3, wherein the material of the organic light-emitting layer is a copolymer.
5. The light-emitting device according to claim 4, wherein the monomer of the copolymer comprises a first compound and a second compound, wherein the first compound is one or more selected from alkylfluorene and alkoxybenzene, and the second compound is one or more selected from 2,1, 3-benzothiadiazole, 2,1, 3-benzoselenadiazole and pyridine.
6. The light emitting device of claim 5, wherein the alkylfluorene is selected from one or more of 2, 7-dibromo-9, 9-behenyl fluorene, 2, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -9, 9-bis (dodecyl) fluorene; and/or
The alkoxybenzene is selected from one or more of 1, 3-didodecyloxy benzene and 5-bromo-1, 2, 3-tri (dodecyloxy) benzene; and/or
The mole percentage content of the first compound in the copolymer is 15-70%; and/or
The mole percentage content of the second compound in the copolymer is 30-85%; and/or
The peak luminescence wavelength of the organic luminescent layer is 650-1200 nm; and/or
The peak luminescence wavelength of the inorganic luminescent layer is 650-1200 nm.
7. The light-emitting device according to claim 1, wherein the first light-emitting unit further comprises a first hole-functional layer provided between the anode and the inorganic light-emitting layer, the first hole-functional layer comprising a first hole-injecting layer and/or a first hole-transporting layer;
The charge generation layer comprises an electron transport layer and a second hole injection layer which are stacked; the electron transport layer is disposed adjacent to the inorganic light emitting layer, and the second hole injection layer is disposed adjacent to the interface modification layer.
8. The light-emitting device according to claim 7, wherein the material of the anode is selected from one or more of doped or undoped metal oxides, carbon silicon materials, metals, composite electrode materials; wherein the doped or undoped metal oxide is selected from one or more of ITO, FTO, ATO, IZO, ITZO, ICO, snO 2、In2O3、Cd:ZnO、Ga:SnO2, AZO, GZO, MZO, AMO; the carbon-silicon material is selected from one or more of silicon, graphite, carbon nano tubes, graphene and carbon fibers; the metal is selected from one or more of Al, ag, cu, mo, au, ba, ca, mg; the composite electrode material is selected from one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS; and/or
The material of the cathode is one or more selected from doped or undoped metal, carbon silicon material, doped or undoped metal oxide and composite electrode material; wherein the doped or undoped metal is selected from one or more of Al、Ag、Cu、Mo、Au、Ba、Ca、Mg、Pt、Ca:Al、LiF:Ca、LiF:Al、BaF2:Al、CsF:Al、CaCO3:Al、BaF2:Ca:Al、Au:Mg、Ag:Mg; the carbon-silicon material is selected from one or more of silicon, graphite, carbon nano tubes, graphene and carbon fibers; the doped or undoped metal oxide is selected from one or more of ITO, FTO, ATO, AZO, GZO, IZO, MZO, AMO; the composite electrode material is selected from one or more of AZO/Ag/AZO、AZO/Al/AZO、ITO/Ag/ITO、ITO/Al/ITO、ZnO/Ag/ZnO、ZnO/Al/ZnO、TiO2/Ag/TiO2、TiO2/Al/TiO2、ZnS/Ag/ZnS、ZnS/Al/ZnS; and/or
The materials of the first hole injection layer and the second hole injection layer are respectively and independently selected from poly (ethylenedioxythiophene): polystyrene sulfonate, poly [9, 9-dioctyl-fluorene-co-N- (4-butylphenyl) -diphenylamine ], polyarylamine, poly (N-vinylcarbazole), polyaniline, polythiophene, polypyrrole, N, N, N ', N' -tetrakis (4-methoxyphenyl) -benzidine, 4-bis [ N- (1-naphthyl) -N-phenyl-amino ] biphenyl, 4 '-tris [ phenyl (m-tolyl) amino ] triphenylamine, 4', one or more of 4 "-tris (N-carbazolyl) -triphenylamine, 1-bis [ (di-4-tolylamino) phenylcyclohexane, tetrafluoro-tetracyano-quinone dimethane doped 4,4',4" -tris (diphenylamino) triphenylamine, p-doped phthalocyanine, F4-TCNQ doped N, N' -diphenyl-N, N '-bis (1-naphthyl) -1,1' -biphenyl-4, 4 "-diamine, hexaazabenzophenanthrene-hexanenitrile; and/or
The material of the first hole transport layer is selected from one or more of arylamine, polyaniline, polyfluorene, polypyrrole, poly (p-phenylene vinylene and its derivatives, copper phthalocyanine, aromatic tertiary amine or polynuclear aromatic tertiary amine, 4 '-bis (p-carbazolyl) -1,1' -biphenyl compound, N, N, N ', N' -tetraarylbenzidine, PEDOT: PSS and its derivatives, poly (N-vinylcarbazole) and its derivatives, polymethacrylate and its derivatives, poly (9, 9-octylfluorene) and its derivatives, poly (spirofluorene) and its derivatives, N, N '-bis (naphthalene-1-yl) -N, N' -diphenyl benzidine, spironpB; and/or
The material of the electron transport layer is one or more selected from inorganic materials and organic materials; wherein the inorganic material is selected from one or more of doped or undoped oxides, doped or undoped semiconductor particles, nitrides, the oxides are selected from one or more of TiO2、ZnO、ZrO2、SnO2、WO3、NiO、Ta2O3、HfO2、Al2O3、ZrSiO4、BaTiO3、BaZrO3、SrTiO3、MgTiO3、TiLiO、ZnMgO、ZnAlO、ZnMgLiO、ZnSnO、ZnLiO、InSnO, the semiconductor particles are selected from one or more of CdS, znSe, znS, the nitrides are selected from Si 3N4, and the doped elements of the oxides and the semiconductor particles are respectively independently selected from one or more of Al, mg, in, li, ga, cd, cs, cu; the organic material is selected from one or more of Alq3, almq3 and DVPBi, TAZ, OXD, PBD, BND, PV; and/or
The material of the inorganic luminescent layer comprises quantum dots, wherein the quantum dots are selected from one or more of single-structure quantum dots, core-shell structure quantum dots and doped or undoped inorganic perovskite type quantum dots; wherein the single-structure quantum dot is selected from one or more of II-VI compound, III-V compound, II-V compound, III-VI compound, IV-VI compound, I-III-VI compound, II-IV-VI compound and IV simple substance, the II-VI compound is selected from one or more of CdSe、CdS、CdTe、ZnSe、ZnS、ZnTe、CdZnS、CdZnSe、CdZnTe、ZnSeS、ZnSeTe、ZnTeS、CdSeS、CdSeTe、CdTeS、CdZnSeS、CdZnSeTe、CdZnSTe, the III-V compound is selected from one or more of InP, inAs, gaP, gaAs, gaN, gaSb, alN, alP, inAsP, inNP, inNSb, gaAlNP, inAlNP, and the IV-VI compound is selected from one or more of PbS, pbSe, pbTe; the I-III-VI compound is selected from one or more of CuInS 2、CuInSe2、AgInS2; the IV group simple substance is selected from one or more of silicon and germanium; the core of the quantum dot with the core-shell structure is selected from any one of the quantum dots with the single structure, and the shell material of the quantum dot with the core-shell structure is selected from one or more of CdS, cdTe, cdSe, cdSeTe, cdZnSe, cdZnS, cdSeS, znSe, znTe, znSeS, znS; the structural general formula of the inorganic perovskite type quantum dot is AMX 3, wherein A is Cs +, M is one or more of Pb2+、Sn2+、Cu2+、Ni2+、Cd2+、Cr2 +、Mn2+、Co2+、Fe2+、Ge2+、Yb2+、Eu2+, and X is one or more of Cl -、Br-、I-.
9. A method of manufacturing a light emitting device, comprising:
Sequentially stacking an anode, a first light-emitting unit, a charge generation layer, an interface modification layer, a second light-emitting unit and a cathode; or sequentially laminating a cathode, a second light-emitting unit, an interface modification layer, a charge generation layer, a first light-emitting unit and an anode;
The first light-emitting unit comprises an inorganic light-emitting layer, the second light-emitting unit comprises an organic light-emitting layer, and the interface modification layer is made of one or more of an insulating material and a hole transport material with HOMO energy level smaller than or equal to-5.8 eV.
10. A display device comprising the light-emitting device according to any one of claims 1 to 8, or comprising the light-emitting device produced by the production method according to claim 9.
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