WO2016187995A1 - 双层掺杂磷光发光器件及其制备方法 - Google Patents

双层掺杂磷光发光器件及其制备方法 Download PDF

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WO2016187995A1
WO2016187995A1 PCT/CN2015/090098 CN2015090098W WO2016187995A1 WO 2016187995 A1 WO2016187995 A1 WO 2016187995A1 CN 2015090098 W CN2015090098 W CN 2015090098W WO 2016187995 A1 WO2016187995 A1 WO 2016187995A1
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layer
light
emitting layer
emitting
emitting device
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陈磊
张晓晋
赖韦霖
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BOE Technology Group Co Ltd
Ordos Yuansheng Optoelectronics Co Ltd
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BOE Technology Group Co Ltd
Ordos Yuansheng Optoelectronics Co Ltd
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Priority to US15/036,190 priority patent/US20170104171A1/en
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/125—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light
    • H10K50/13—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers specially adapted for multicolour light emission, e.g. for emitting white light comprising stacked EL layers within one EL unit
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    • H10K50/14—Carrier transporting layers
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    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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Definitions

  • At least one embodiment of the invention relates to a dual layer doped phosphorescent light emitting device and a method of fabricating the same.
  • OLEDs organic light emitting displays
  • EL organic electroluminescence
  • full-color organic EL displays people are increasingly demanding displays.
  • the luminous efficiency and color purity of RGB three primary colors have always been the focus and difficulty of research.
  • the active matrix organic light emitting diode (AMOLED) display currently uses a phosphorescent doping mechanism in the red light emitting unit (R) and the green light emitting unit (G).
  • the host material in the phosphorescence doping luminescence mechanism requires high exciton yield, good charge transport performance, strong chemical and thermal stability, and high glass transition temperature (>120 ° C). It is also necessary to consider whether the T1 state energy level matches the guest material.
  • blue wide bandgap materials are preferred as the main body of R, G, and B, and energy level matching needs to be considered for better energy conversion.
  • the main body of the doping mechanism is currently divided into single-body doping and dual-body doping.
  • the single-body doping process has low requirements and is simple to prepare.
  • the balance of carriers is largely restricted by the carrier transport properties of the host material.
  • the electron transport of most materials is unbalanced, causing the center of the luminescence to deviate from the center of the Emitting Layer (EML).
  • Excitons diffuse to the interface, causing polaron quenching.
  • Co-host doping includes independent dual-body doping as well as pre-mixed dual-body doping.
  • the independent double-body doping is to prepare a light-emitting layer by co-evaporating two kinds of host materials of a hole type and an electron type with a phosphorescent dopant.
  • the advantage is that the carrier of the two transmission performance bodies is transported relative to the carrier of the single body balanceable portion, so that the illuminating center approaches the center of the luminescent layer.
  • the performance of the independent dual-body doping system device is largely limited by the two body doping ratios.
  • the change in the doping ratio has a large effect on the efficiency of the device. Therefore, the stability of the evaporation process is required to be high.
  • the two bodies may interact after mixing to form an exciplex, which causes quenching of the host excitons, resulting in a decrease in device performance.
  • Pre The pre-mixed double-body doping is to mix the two main materials and then put them into the crucible for evaporation.
  • At least one embodiment of the present invention provides a dual-layer doped phosphorescent light-emitting device and a method of fabricating the same.
  • the double-layer doped phosphorescent light-emitting device comprises a double-layer light-emitting layer, which can avoid the problem of poor device repeatability caused by fluctuations of the process doping ratio caused by the three-source co-steaming in the independent dual-body doping and the pre-mixed double Limitation of material selection in bulk doping.
  • At least one embodiment of the present invention provides a dual-layer doped phosphorescent light emitting device comprising a double-layered light-emitting layer, wherein the double-layer light-emitting layer includes a first light-emitting layer and a second light-emitting layer, the first light-emitting layer and the first light-emitting layer
  • the two luminescent layers each comprise a host material and a guest material, the host material of the first luminescent layer is a hole-type host material, and the host material of the second luminescent layer is an electronic body material.
  • the thickness of the first light-emitting layer corresponds to the hole mobility of the hole-type host material
  • the thickness of the second light-emitting layer corresponds to the electronic body The electron mobility of the material.
  • the thicknesses of the first light-emitting layer and the second light-emitting layer are different.
  • the first light-emitting layer and the second light-emitting layer have a total thickness of 20-40 nm.
  • the double-layer doped phosphorescent light-emitting device further includes a hole transporting layer, wherein the hole-type host material is different from the hole transporting material of the hole transporting layer.
  • the host material of the first light-emitting layer includes a material containing a carbazole group
  • the material containing the carbazole group includes 4, 4'-N, N'- Dicarbazole biphenyl (CBP), 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA) and 9,9'-(1,3-phenyl)di-9H-indole
  • mCP the hole transport layer material comprising N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'- Diphenyl-4,4'-diamine
  • NPB N-N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'- Diphenyl-4,4'-diamine
  • m-MTDATA 4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine
  • the double-layer doped phosphorescent light-emitting device further includes an electron transport layer, wherein the electron-type host material is different from the electron transport material of the electron transport layer.
  • the host material of the second light-emitting layer includes bis(2-methyl-8-hydroxyquinoline)(4-lbiphenoxy)aluminum (BAlq), 2 ,4,6-tris(9H-carbazol-9-yl)-1,3,5-triazine (TRZ) and 2,7-bis(diphenyl-phosphine oxide)-9,9-dimethyl Any one of cerium (PO6), the electron transport layer material comprising 4,7-diphenyl-1,10-phenanthroline (BPhen), 1,3,5-tris(1-phenyl) Any one of -1H-benzimidazol-2-yl)benzene (TPBI) and an n-type doped electron transport material.
  • BAlq bis(2-methyl-8-hydroxyquinoline)(4-lbiphenoxy)aluminum
  • TRZ 2,4,6-tris(9H-carbazol-9-yl)-1,3,5-triazine
  • TRZ 2,7-bis(diphenyl
  • the guest materials of the first light-emitting layer and the second light-emitting layer are the same phosphorescent dopant, and the phosphorescent dopant includes a red phosphorescent material and a green phosphorescent material. Any one.
  • the red phosphorescent material includes octaethylporphyrin platinum (PtOEP), bis(2-(2'-benzothienyl)pyridine-N, C3') (acetyl Acetone) hydrazine [(btp) 2 Ir(acac)], tris(dibenzoylmethane)mono(phenanthroline) ruthenium (III) [Eu(dbm) 3 (Phen)], tris[1-phenyl Isoquinoline-C2,N] ⁇ (III)(Ir(piq) 3 ), bis(1-phenylisoquinoline)(acetylacetonate) ruthenium(III)[Ir(piq) 2 (acac)] Any of them;
  • PtOEP octaethylporphyrin platinum
  • the green phosphorescent material includes tris(2-phenylpyridine) ruthenium (Ir(ppy) 3 ), bis(2-phenylpyridine) acetylacetonate [Ir(ppy) 2 (acac)], and three (2) -Phenylpyridine) ruthenium (III) (Ir(mppy) 3 ), bis(2-(4-fluorophenyl)-4-phenylpyridine) acetylacetonate [Ir(FPP) 2 (acac)] And tris(4-tert-butyl-2-phenylpyridine) ruthenium (Ir(Bu-ppy) 3 ).
  • At least one embodiment of the present invention further provides a method for fabricating a dual-layer doped phosphorescent light-emitting device, comprising forming a double-layer light-emitting layer, wherein the forming a double-layer light-emitting layer includes forming a first light-emitting layer and forming a second light-emitting layer,
  • the first luminescent layer and the second luminescent layer each comprise a host material and a guest material, the host material of the first luminescent layer is a hole type host material, and the host material of the second luminescent layer is an electronic body material.
  • the first light-emitting layer and the second light-emitting layer are both formed by co-evaporation of two sources.
  • the first light-emitting layer is determined by hole mobility of the hole-type host material and electron mobility of the electron-type host material. And a thickness of the second luminescent layer.
  • the method of fabricating the double-layer doped phosphorescent light-emitting device further includes forming a hole transporting layer, wherein the hole-type host material is different from the hole transporting material of the hole transporting layer.
  • the host material of the first light-emitting layer includes a material containing a carbazole group, and the material containing the carbazole group includes 4, 4'-N.
  • N'-dicarbazole biphenyl CBP
  • 4,4',4"-tris(carbazol-9-yl)triphenylamine TCTA
  • 4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine m-MTDATA
  • 2-[N-(4-carbazolylphenyl)-N-phenylamino]biphenyl CBP
  • CBP N'-dicarbazole biphenyl
  • TCTA 4,4',4"-tris(carbazol-9-yl)triphenylamine
  • mCP the hole transport layer material comprising N,
  • the method of fabricating the dual-layer doped phosphorescent light-emitting device further includes forming an electron transport layer, wherein the electron-type host material is different from the electron transport material of the electron transport layer.
  • the host material of the second light-emitting layer comprises bis(2-methyl-8-hydroxyquinoline)(4-lbiphenoxy)aluminum (BAlq) ), 2,4,6-tris(9H-carbazol-9-yl)-1,3,5-triazine (TRZ) and 2,7-bis(diphenyl-phosphine oxide)-9,9- Any one of dimethyl hydrazine (PO6), the electron transport layer material comprising 4,7-diphenyl-1,10-phenanthroline (BPhen), 1,3,5-tri (1) -Phenyl-1H-benzimidazol-2-yl)benzene (TPBI) and an n-type doped electron transport material.
  • BAlq bis(2-methyl-8-hydroxyquinoline)(4-lbiphenoxy)aluminum
  • TRZ 2,4,6-tris(9H-carbazol-9-yl)-1,3,5-triazine
  • TRZ 2,7-bis(diphenyl-phos
  • the guest materials of the first light-emitting layer and the second light-emitting layer are the same phosphorescent dopant, and the phosphorescent dopant includes a red phosphorescent material and a green phosphorescent light. Any of the materials.
  • the red phosphorescent material comprises octaethylporphyrin platinum (PtOEP), bis(2-(2'-benzothienyl)pyridine-N, C3' (acetylacetone) ruthenium [(btp) 2 Ir(acac)], tris(dibenzoylmethane)mono(phenanthroline) ruthenium (III) [Eu(dbm) 3 (Phen)], three [1] -Phenylisoquinoline-C2,N] ⁇ (III)(Ir(piq) 3 ), bis(1-phenylisoquinoline)(acetylacetonate) ruthenium(III)[Ir(piq) 2 (acac Any one of them];
  • PtOEP octaethylporphyrin platinum
  • PtOEP bis(2-(2'-benzothienyl)pyridine-N
  • the green phosphorescent material includes tris(2-phenylpyridine) ruthenium (Ir(ppy) 3 ), bis(2-phenylpyridine) acetylacetonate [Ir(ppy) 2 (acac)], and three (2) -Phenylpyridine) ruthenium (III) (Ir(mppy) 3 ), acetylacetonate bis(2-(4-fluorophenyl)-4-phenylpyridine) hydrazine [Ir(FPP) 2 (acac)] And tris(4-tert-butyl-2-phenylpyridine) ruthenium (Ir(Bu-ppy) 3 ).
  • FIG. 1 is a schematic structural view (normal structure) of a double-layer doped phosphorescent light-emitting device according to an embodiment of the present invention
  • FIG. 2 is a schematic structural view (inverted structure) of a double-layer doped phosphorescent light-emitting device according to another embodiment of the present invention.
  • FIG. 3 is a schematic structural view (transparent structure) of a double-layer doped phosphorescent light-emitting device according to another embodiment of the present invention.
  • At least one embodiment of the present invention provides a dual-layer doped phosphorescent light-emitting device, as shown in FIG. 1 , comprising a double-layer light-emitting layer 13 , wherein the double-layer light-emitting layer 13 includes a first light-emitting layer 131 and a second light-emitting layer 132 .
  • the first light-emitting layer 131 and the second light-emitting layer 132 each include a host material and a guest material, the host material of the first light-emitting layer 131 is a hole-type host material, and the host material of the second light-emitting layer 132 is an electron-type host material.
  • the first light-emitting layer and the second light-emitting layer can be respectively formed by co-evaporation of two sources, thereby avoiding poor device repeatability caused by fluctuations of the process doping ratio caused by three-source co-steaming in independent double-body doping. Problems and limitations on material selection in pre-mixed dual-body doping.
  • the thickness of the first luminescent layer may correspond to the hole mobility of the hole-type host material
  • the thickness of the second luminescent layer may correspond to the electron mobility of the electron-type host material.
  • the thicknesses of the first light-emitting layer 131 and the second light-emitting layer 132 may be adjusted according to the hole mobility of the hole-type host material and the electron mobility of the electron-type host material, respectively. For example, in the case where the hole mobility of the hole-type host material is high, the first light-emitting layer having a relatively large thickness is used correspondingly, and if the hole mobility of the hole-type host material is low, a correspondingly small thickness is adopted.
  • the first luminescent layer is adjusted according to the hole mobility of the hole-type host material and the electron mobility of the electron-type host material, respectively. For example, in the case where the hole mobility of the hole-type host material is high, the first light-emitting layer having a relatively large thickness is used correspondingly, and if the hole mobility of the
  • the thickness of the second luminescent layer can also be adjusted in a similar manner.
  • a second light-emitting layer having a relatively large thickness is used correspondingly.
  • a second light-emitting layer having a smaller thickness is used correspondingly.
  • the thicknesses of the first luminescent layer 131 and the second luminescent layer 132 are generally different.
  • the recombination center of the excitons can be made on the interface region of the first luminescent layer 131 and the second luminescent layer 132 by the thickness control of the first luminescent layer 131 and the second luminescent layer 132 to ensure that the diffusion range of the excitons is in two layers. In the region of the luminescent layer, the quenching caused by the diffusion of excitons to other layers is avoided, and the use of the electron blocking layer can be omitted.
  • the first luminescent layer 131 and the second luminescent layer 132 have a total thickness of about 20-40 nm.
  • the double-layer doped phosphorescent light-emitting device can control the transport of carriers by adjusting the thicknesses of the two light-emitting layers respectively, thereby ensuring that the diffusion range of the excitons is in the two light-emitting layer regions, thereby avoiding the diffusion of excitons to other layers. Quenching eliminates the use of electronic barriers.
  • the double-layer doped phosphorescent light-emitting device may further include a hole transport layer 11 and the hole-type host material is different from the hole transport material of the hole transport layer 11 (the hole-type host material and the hole of the first light-emitting layer)
  • the transport layer has different hole transport materials).
  • the double layer doped phosphorescent light emitting device can be optimized for life, and thus, the double layer doped phosphorescent light emitting device can Has a long service life.
  • the double-layer doped phosphorescent light-emitting device may further include an electron transport layer 12, and the electron-type host material is different from the electron transport material of the electron transport layer 12 (the electron-type host material of the second light-emitting layer and the electron transport material of the electron transport layer) different).
  • the double-layer doped phosphorescent light-emitting device can optimize the life, so that the double-layer doped phosphorescent light-emitting device can have a long service life.
  • the host material of the first light-emitting layer 131 includes a material containing a carbazole group.
  • carbazole-containing materials include 4,4'-N,N'-dicarbazole biphenyl (CBP), 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA). And any one of 9,9'-(1,3-phenyl)di-9H-carbazole (mCP), but is not limited thereto.
  • the material of the hole transport layer 11 includes N,N'-bis(1-naphthyl)-N,N'-diphenyl-1,1'-diphenyl-4,4'-diamine (NPB). , 4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA) and 4,4-2-[N-(4-carbazolephenyl) Any one of -N-phenylamino]biphenyl (CPB), but is not limited thereto, and has a thickness of, for example, about 20 to 70 nm.
  • the host material of the second light-emitting layer 132 includes bis(2-methyl-8-hydroxyquinoline)(4-lbiphenoxy)aluminum (BAlq), 2,4,6-tris(9H-carbazole). -9-yl)-1,3,5-triazine (TRZ) and 2,7-bis(diphenyl-phosphine oxide)-9,9-dimethylhydrazine (PO6), but Not limited to this.
  • the material of the electron transport layer 12 includes 4,7-diphenyl-1,10-phenanthroline (BPhen), 1,3,5-tris(1-phenyl-1H-benzimidazole-2- Any one of benzene (TPBI) and n-doping electron transport materials, but is not limited thereto, and has a thickness of, for example, about 10 to 30 nm.
  • the n-type doped electron transporting material includes, for example, 2,9-dimethyl-4,7-biphenyl-1,10-phenanthroline (BCP): Li 2 CO 3 , 8-hydroxyquinoline aluminum (Alq3) ): Mg, TPBI: Li, etc., but is not limited thereto.
  • the guest materials of the first luminescent layer 131 and the second luminescent layer 132 are the same phosphorescent dopant, so that monochromatic light can be emitted, and a monochromatic luminescent device can be formed.
  • the phosphorescent dopant doping content in the first light-emitting layer 131 and the second light-emitting layer 132 is less than 10% by mass.
  • the phosphorescent dopant includes any one of a red phosphorescent material and a green phosphorescent material.
  • red phosphorescent materials include octaethylporphyrin platinum (PtOEP), bis(2-(2'-benzothienyl)pyridine-N, C3') (acetylacetone) ruthenium [(btp) 2 Ir (acac) )], tris(dibenzoylmethane)mono(phenanthroline)iridium(III)[Eu(dbm) 3 (Phen)], tris[1-phenylisoquinoline-C2,N]indole (III) (Ir(piq) 3 ), bis(1-phenylisoquinoline) (acetylacetonate) ruthenium (III) [Ir(piq) 2 (acac)], but is not limited thereto.
  • PtOEP octaethylporphyrin platinum
  • PtOEP bis(2-(2'-benzothienyl)pyridine-N, C3'
  • the green phosphorescent material includes tris(2-phenylpyridine) ruthenium (Ir(ppy) 3 ), bis(2-phenylpyridine) acetylacetonate [Ir(ppy) 2 (acac)], and three (2) -Phenylpyridine) ruthenium (III) (Ir(mppy) 3 ), bis(2-(4-fluorophenyl)-4-phenylpyridine) acetylacetonate [Ir(FPP) 2 (acac)] And tris(4-tert-butyl-2-phenylpyridine) ruthenium (Ir(Bu-ppy) 3 ), but is not limited thereto.
  • the double-layer doped phosphorescent light-emitting device may further include a hole injection layer, a cathode and an anode, and
  • the structure may include an electron injection layer or the like, and the structure of the double-layer doped phosphorescent light-emitting device may be a normal structure, an inverted structure, or a transparent structure.
  • Fig. 1 shows a double-layer doped phosphorescent light-emitting device of a normal structure.
  • the double-layer doped phosphorescent light-emitting device comprises a first light-emitting layer 131, a second light-emitting layer 132, a hole transport layer 11 and an electron transport layer 12, and each layer material can be as described above, and further includes a cathode 14, an anode 15, and a cavity.
  • the layer 16 is injected.
  • the cathode 14 may be a Mg:Ag alloy (Mg-Ag alloy) having a thickness of, for example, about 10 to 150 nm (a suitable thickness may be selected depending on the type of the device).
  • the anode 15 may be made of indium tin oxide (ITO), and the thickness of the ITO anode is, for example, about 10 to 150 nm.
  • the hole injection layer 16 may be a metal oxide MeO such as MoO 3 or a p-type doped MeO (metal oxide)-TPD (N,N'-bis(3-methylphenyl)-N, N'-diphenyl-1,1'-diphenyl-4,4'-diamine): F4TCNQ(N,N,N',N'-tetramethoxyphenyl)-p-diaminobiphenyl : 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl p-benzoquinone) or m-MTDATA: F4TCNQ (4,4',4"-three (N- 3-methylphenyl-N-phenylamino)triphenylamine: 2,3,5,6-tetrafluor
  • a normally-structured two-layer doped green phosphorescent light-emitting device anode ITO 150 nm/m-MTDATA: F4TCNQ 30 nm/m-MTDATA 60 nm/CBP: Ir(ppy) 3 7% 24 nm/BAlq: Ir(ppy) 3 7 % 16 nm / BPhen 10 nm / Mg: Ag 100 nm (cathode).
  • a normally-structured two-layer doped red phosphorescent light-emitting device anode ITO 150 nm/m-MTDATA: F4TCNQ 30 nm/m-MTDATA 60 nm/CBP: Ir(piq) 2 (acac) 7% 24 nm/BAlq: Ir (piq 2 (acac) 7% 16 nm / BPhen 10 nm / Mg: Ag 100 nm (cathode).
  • Figure 2 shows a schematic diagram of a two-layer doped phosphorescent light emitting device of inverted structure.
  • the double-layer doped phosphorescent light-emitting device includes a first light-emitting layer 131, a second light-emitting layer 132, a hole transport layer 11, and an electron transport layer 12.
  • the material of each layer can be as described above.
  • the electron transport layer 12 It is an n-type doped electron transport layer, but is not limited thereto.
  • the double-layer doped phosphorescent light-emitting device further includes a cathode 14, an anode 15, and a hole injection layer 16.
  • the cathode 14 can adopt ITO
  • the anode 15 can adopt Mg:Ag alloy
  • the material and thickness of the hole injection layer 16 and the like can be referred to in the double-layer doped phosphorescent light-emitting device of the normal structure, and details are not described herein again.
  • an inverted structure of a two-layer doped green phosphorescent light-emitting device cathode ITO 150 nm / BCP: Li 2 CO 3 10 nm / BAlq: Ir (ppy) 3 7% 16 nm / CBP: Ir (ppy) 3 7% 24 nm / CPB 40 nm / MoO 3 1 nm / Mg: Ag 100 nm (anode).
  • an inverted phosphorescent light emitting device cathode ITO 150 nm / BCP: Li 2 CO 3 10 nm / BAlq: Ir (piq) 2 (acac) 7% 16 nm / CBP: Ir (piq) 2 (acac) 7% 24 nm / NPB 40 nm / MoO 3 1 nm / Mg: Ag 100 nm (anode).
  • Figure 3 shows a schematic diagram of a two-layer doped phosphorescent light-emitting device of a transparent structure.
  • the double-layer doped phosphorescent light-emitting device includes a first light-emitting layer 131, a second light-emitting layer 132, a hole transport layer 11 and an electron transport layer 12, and further includes a cathode 14, an anode 15, a hole injection layer 16, and a protective layer 17.
  • the cathode 14 may be made of Mg:Ag alloy or ITO
  • the anode 15 may be made of ITO, a hole injection layer 16, a hole transport layer, an electron transport layer, and a material of the host material and the guest material of the first light-emitting layer and the second light-emitting layer.
  • the protective layer 17 may be, for example, a metal oxide or a polymer material, wherein the metal oxide includes, for example, MoO 3 , and the polymer material includes, for example, PEDOT:PSS [polydioxyethylthiophene-polystyrenesulfonic acid].
  • the protective layer 17 may not be provided.
  • An embodiment of the present invention further provides a method for fabricating a dual-layer doped phosphorescent light-emitting device, comprising forming a double-layer light-emitting layer 13, wherein the double-layer light-emitting layer 13 includes a first light-emitting layer 131 and a second light-emitting layer 132, first The light-emitting layer 131 and the second light-emitting layer 132 each include a host material and a guest material, the host material of the first light-emitting layer 131 is a hole-type host material, and the host material of the second light-emitting layer 132 is an electron-type host material.
  • the double-layer light-emitting layer can ensure that the diffusion range of the excitons is in the two light-emitting layer regions, avoiding the quenching caused by the diffusion of excitons to other layers, and the use of the electron blocking layer is omitted.
  • both the first luminescent layer and the second luminescent layer can be formed by co-evaporation of two sources.
  • the preparation method is simple. The problem of poor device repeatability due to fluctuations in process doping ratio due to fluctuations in process doping ratio due to tri-source co-steaming in independent dual-body doping and the limitation of material selection in pre-mixed dual-body doping can be avoided.
  • the thicknesses of the first light-emitting layer 131 and the second light-emitting layer 132 can be determined by the hole mobility of the hole-type host material and the electron mobility of the electron-type host material.
  • the composite region of the excitons may be on the interface region of the first luminescent layer and the second luminescent layer by controlling the thicknesses of the first luminescent layer and the second luminescent layer.
  • carrier transport can be controlled by separately adjusting the thicknesses of the two light-emitting layers, thereby ensuring that the diffusion range of the excitons is in the two light-emitting layer regions, and the quenching caused by the diffusion of excitons to other layers is avoided. Eliminate the use of electronic barriers.
  • the method further includes forming a hole transport layer 11 in which the hole type host material is different from the hole transport material of the hole transport layer 11.
  • the hole type host material is different from the hole transport material of the hole transport layer 11, and
  • the double-layer doped phosphorescent light-emitting device is advantageous for life optimization, so that the double-layer doped phosphorescent light-emitting device can have a long service life.
  • the method further includes forming an electron transport layer 12, wherein the electron type host material is different from the electron transport material of the electron transport layer 12.
  • the electronic type host material is different from the electron transport material of the electron transport layer 12, so that the double-layer doped phosphorescent light-emitting device can be optimized for life, and thus, the double-layer doped phosphorescent light-emitting device can have a long service life.
  • the selection of the host material and the guest material of the first light-emitting layer 131 and the second light-emitting layer 132, the selection of the hole transport layer and the electron transport layer material, the doping amount of the guest material, the first light-emitting layer 131, and The thickness and the like of the second light-emitting layer 132 can be referred to the contents given in the above double-layer doped phosphorescent light-emitting device.
  • the phosphorescent dopant doping content in the examples of the present invention refers to the mass percentage.
  • the substances used in the examples of the present invention are all commonly used in the art, and the abbreviations or the full names of the substances represented by the abbreviations are given in parentheses before or after the substance for convenience of understanding.
  • At least one embodiment of the present invention provides a dual-layer doped phosphorescent light-emitting device including a double-layer light-emitting layer, wherein the double-layer light-emitting layer includes a first light-emitting layer and a second light-emitting layer, and a method of fabricating the same
  • the layer, the first luminescent layer and the second luminescent layer each comprise a host material and a guest material, the host material of the first luminescent layer is a hole-type host material, and the host material of the second luminescent layer is an electronic body material.
  • the double-layer doped phosphorescent light-emitting device can avoid the problem of poor device repeatability due to fluctuation of process doping ratio caused by three-source co-steaming in independent dual-body doping and material selection in pre-mixed dual-body doping limits.

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Abstract

一种双层掺杂磷光发光器件及其制备方法。该双层掺杂磷光发光器件包括双层发光层(13)，其中，所述双层发光层包括第一发光层(131)和第二发光层(132)，所述第一发光层(131)和第二发光层(12)均包括主体材料和客体材料，所述第一发光层(131)的主体材料为空穴型主体材料，所述第二发光层(132)的主体材料为电子型主体材料。该双层掺杂磷光发光器件可以避免独立双主体掺杂中三源共蒸带来的因工艺掺杂比例的波动而导致的器件重复性能差的问题以及预混合的双主体掺杂中材料选择的限制。

Description

双层掺杂磷光发光器件及其制备方法 技术领域
本发明至少一实施例涉及一种双层掺杂磷光发光器件及其制备方法。
背景技术
近年来，有机电致发光显示器(Organic Light Emitting Display，OLED)作为新一代的显示技术倍受瞩目。特别是最近几年有机电致发光(Electroluminescence，EL)器件制作工艺的不断改进和完善，全彩色有机EL显示器的量产，其巨大的商业化前景已逐渐显现。随着全彩有机EL显示器的出现，人们对显示的要求越来越高。特别是RGB三基色的发光效率和色纯度一直是研究的重点和难点。
为了提高效率，目前有源矩阵有机发光二极管面板(Active Matrix Organic Light Emitting Diode，AMOLED)显示中红色发光单元(R)和绿色发光单元(G)多采用磷光掺杂发光机制。磷光掺杂发光机制中的主体材料要求激子产率较高，电荷传输性能好，化学性质及热稳定性强，玻璃化温度高(>120℃)。还需考虑与客体(Guest)材料的T1态能级是否匹配。一般倾向于采用蓝色宽带隙材料作为R、G、B的主体，同时需考虑能级的匹配以更好的能量转换。
掺杂机制的主体目前分为单主体掺杂、双主体掺杂。单主体掺杂的工艺要求低，制备较简单。载流子的平衡与否很大程度受主体(Host)材料载流子传输性质的制约，绝大多数材料空穴电子传输不平衡，从而导致发光中心偏离发光层(Emitting layer，EML)中央，激子扩散至界面，引发激子淬灭(polaron quenching)。双主体(co-host)掺杂包括独立双主体掺杂以及预混合(pre-mix)的双主体掺杂。独立双主体掺杂是将空穴型和电子型的两种主体材料加上磷光掺杂剂(dopant)三源共蒸镀的方式制备发光层。其优势是两种传输性能主体的加入相对于单主体可平衡部分的载流子传输，使发光中心趋近于发光层中心。但是独立双主体掺杂体系器件的性能很大程度受限于两种主体掺杂比例。掺杂比例的改变会对器件的效率有很大程度的影响。因此对蒸镀工艺的稳定性要求较高。另外，两种主体混合后还可能相互作用，形成激基复合物(exciplex)，对主体激子造成猝灭，使得器件性能下降。预 混合(pre-mix)的双主体掺杂是将两种主体材料先混合好，然后放进坩埚中蒸镀，这要求两种主体材料的蒸镀温度要极度的相近才能保证两者的混合比例不变。开发和寻找蒸镀温度相同、性能优越的双主体材料存在很大的困难，故而很大程度限制了器件的结构设计和性能优化。无论是单主体掺杂还是双主体掺杂(包括独立双主体掺杂以及预混合的双主体掺杂)都很难控制激子的复合(Recombination)和扩散中心在发光层中心，因此目前多加入电子阻挡层(Electron-Blocking Layer，EBL)。而电子阻挡层的加入不但增加驱动电压，也使器件的设计和制备变的复杂化。
发明内容
本发明至少一实施例提供一种双层掺杂磷光发光器件及其制备方法。该双层掺杂磷光发光器件包括双层发光层，可以避免独立双主体掺杂中三源共蒸带来的因工艺掺杂比例的波动而导致的器件重复性能差的问题以及预混合的双主体掺杂中材料选择的限制。
本发明至少一实施例提供一种双层掺杂磷光发光器件，包括双层发光层，其中，所述双层发光层包括第一发光层和第二发光层，所述第一发光层和第二发光层均包括主体材料和客体材料，所述第一发光层的主体材料为空穴型主体材料，所述第二发光层的主体材料为电子型主体材料。
例如，该双层掺杂磷光发光器件中，所述第一发光层的厚度对应于所述空穴型主体材料的空穴迁移率，所述第二发光层的厚度对应于所述电子型主体材料的电子迁移率。
例如，该双层掺杂磷光发光器件中，所述第一发光层和所述第二发光层的厚度不同。
例如，该双层掺杂磷光发光器件中，所述第一发光层和第二发光层总厚度为20-40nm。
例如，该双层掺杂磷光发光器件还包括空穴传输层，其中，所述空穴型主体材料不同于空穴传输层的空穴传输材料。
例如，该双层掺杂磷光发光器件中，所述第一发光层的主体材料包括含咔唑基团的材料，所述含咔唑基团的材料包括4,4'-N,N'-二咔唑联苯(CBP)、4,4',4”-三(咔唑-9-基)三苯胺(TCTA)和9,9’-(1,3-苯基)二-9H-咔唑(mCP)中的任意一种，所述空穴传输层材料包括N,N’-双(1-萘基)-N,N’-二苯基-1,1’- 二苯基-4,4’-二胺(NPB)、4,4′,4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺(m-MTDATA)和4,4-2-[N-(4-咔唑苯基)-N-苯基氨基]联苯(CPB)中的任意一种。
例如，该双层掺杂磷光发光器件还包括电子传输层，其中，所述电子型主体材料不同于所述电子传输层的电子传输材料。
例如，该双层掺杂磷光发光器件中，所述第二发光层的主体材料包括双(2-甲基-8-羟基喹啉)(4-l联苯氧基)铝(BAlq)、2,4,6-三(9H-咔唑-9-基)-1,3,5-三嗪(TRZ)和2,7-双(二苯基-氧化膦)-9,9-二甲基芴(PO6)中的任意一种，所述电子传输层材料包括4,7-二苯基-1,10-邻二氮杂菲(BPhen)、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBI)和n型掺杂电子传输材料中的任意一种。
例如，该双层掺杂磷光发光器件中，所述第一发光层和第二发光层的客体材料为同一种磷光掺杂剂，所述磷光掺杂剂包括红色磷光材料和绿色磷光材料中的任意一种。
例如，该双层掺杂磷光发光器件中，所述红色磷光材料包括八乙基卟啉铂(PtOEP)、双(2-(2'-苯并噻吩基)吡啶-N,C3')(乙酰丙酮)合铱[(btp)2Ir(acac)]、三(二苯甲酰基甲烷)单(菲罗啉)铕(III)[Eu(dbm)3(Phen)]、三[1-苯基异喹啉-C2,N]铱(III)(Ir(piq)3)、二(1-苯基异喹啉)(乙酰丙酮)合铱(III)[Ir(piq)2(acac)]中的任意一种；
所述绿色磷光材料包括三(2-苯基吡啶)合铱(Ir(ppy)3)、乙酰丙酮酸二(2-苯基吡啶)铱[Ir(ppy)2(acac)]、三(2-苯基吡啶)合铱(III)(Ir(mppy)3)、乙酰丙酮酸二(2-(4-氟苯基)-4-苯基吡啶)铱[Ir(FPP)2(acac)]、三(4-特丁基-2-苯基吡啶)合铱(Ir(Bu-ppy)3)中的任意一种。
本发明至少一实施例还提供一种双层掺杂磷光发光器件的制备方法，包括形成双层发光层，其中，所述形成双层发光层包括形成第一发光层和形成第二发光层，所述第一发光层和第二发光层均包括主体材料和客体材料，所述第一发光层的主体材料为空穴型主体材料，所述第二发光层的主体材料为电子型主体材料。
例如，该双层掺杂磷光发光器件的制备方法中，所述第一发光层和第二发光层均通过两源共蒸形成。
例如，该双层掺杂磷光发光器件的制备方法中，通过所述空穴型主体材料的空穴迁移率和所述电子型主体材料的电子迁移率来确定所述第一发光层 和所述第二发光层的厚度。
例如，该双层掺杂磷光发光器件的制备方法中，其中，通过控制所述第一发光层和第二发光层的厚度，使激子的复合区域在所述第一发光层和所述第二发光层的界面区域上。
例如，该双层掺杂磷光发光器件的制备方法还包括形成空穴传输层，其中，所述空穴型主体材料不同于空穴传输层的空穴传输材料。
例如，该双层掺杂磷光发光器件的制备方法中，所述第一发光层的主体材料包括含咔唑基团的材料，所述含咔唑基团的材料包括4,4'-N,N'-二咔唑联苯(CBP)、4,4',4”-三(咔唑-9-基)三苯胺(TCTA)和9,9’-(1,3-苯基)二-9H-咔唑(mCP)中的任意一种，所述空穴传输层材料包括N,N’-双(1-萘基)-N,N’-二苯基-1,1’-二苯基-4,4’-二胺(NPB)、4，4′，4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺(m-MTDATA)和4,4-2-[N-(4-咔唑苯基)-N-苯基氨基]联苯(CPB)中的任意一种。
例如，该双层掺杂磷光发光器件的制备方法还包括形成电子传输层，其中，所述电子型主体材料不同于所述电子传输层的电子传输材料。
例如，该双层掺杂磷光发光器件的制备方法中，所述第二发光层的主体材料包括双(2-甲基-8-羟基喹啉)(4-l联苯氧基)铝(BAlq)、2,4,6-三(9H-咔唑-9-基)-1,3,5-三嗪(TRZ)和2,7-双(二苯基-氧化膦)-9,9-二甲基芴(PO6)中的任意一种，所述电子传输层材料包括4,7-二苯基-1,10-邻二氮杂菲(BPhen)、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBI)和n型掺杂电子传输材料中的任意一种。
例如，该双层掺杂磷光发光器件的制备方法中，所述第一发光层和第二发光层的客体材料为同一种磷光掺杂剂，所述磷光掺杂剂包括红色磷光材料和绿色磷光材料中的任意一种。
例如，该双层掺杂磷光发光器件的制备方法中，所述红色磷光材料包括八乙基卟啉铂(PtOEP)、双(2-(2'-苯并噻吩基)吡啶-N,C3')(乙酰丙酮)合铱[(btp)2Ir(acac)]、三(二苯甲酰基甲烷)单(菲罗啉)铕(III)[Eu(dbm)3(Phen)]、三[1-苯基异喹啉-C2,N]铱(III)(Ir(piq)3)、二(1-苯基异喹啉)(乙酰丙酮)合铱(III)[Ir(piq)2(acac)]中的任意一种；
所述绿色磷光材料包括三(2-苯基吡啶)合铱(Ir(ppy)3)、乙酰丙酮酸二(2-苯基吡啶)铱[Ir(ppy)2(acac)]、三(2-苯基吡啶)合铱(III)(Ir(mppy)3)、乙酰丙酮酸 二(2-(4-氟苯基)-4-苯基吡啶)铱[Ir(FPP)2(acac)]、三(4-特丁基-2-苯基吡啶)合铱(Ir(Bu-ppy)3)中的任意一种。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例的附图作简单地介绍，显而易见地，下面描述中的附图仅仅涉及本发明的一些实施例，而非对本发明的限制。
图1为本发明一实施例提供的双层掺杂磷光发光器件结构示意图(正常结构)；
图2为本发明另一实施例提供的双层掺杂磷光发光器件结构示意图(倒置结构)；
图3为本发明另一实施例提供的双层掺杂磷光发光器件结构示意图(透明结构)；
附图标记：
10-玻璃基板；11-空穴传输层(Hole Transport Layer，HTL)；12-电子传输层(Electron Transport Layer，ETL)；13-双层发光层；131-第一发光层；132-第二发光层；14-阴极；15-阳极；16-空穴注入层(Hole Injection Layer，HIL)；17-保护层。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例的附图，对本发明实施例的技术方案进行清楚、完整地描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明至少一实施例提供一种双层掺杂磷光发光器件，如图1所示，包括双层发光层13，其中，双层发光层13包括第一发光层131和第二发光层132，第一发光层131和第二发光层132均包括主体材料和客体材料，第一发光层131的主体材料为空穴型主体材料，第二发光层132的主体材料为电子型主体材料。
设置双层发光层，可使激子的扩散范围在两层发光层区域内，避免激子 扩散到其他层引起的淬灭，省去电子阻挡层的使用。而且第一发光层和第二发光层可分别采用两源共蒸形成，从而可以避免独立双主体掺杂中三源共蒸带来的因工艺掺杂比例的波动而导致的器件重复性能差的问题以及预混合的双主体掺杂中对材料选择的限制。
例如，第一发光层的厚度可对应于空穴型主体材料的空穴迁移率，第二发光层的厚度可对应于电子型主体材料的电子迁移率。例如，第一发光层131和第二发光层132的厚度可分别根据空穴型主体材料的空穴迁移率和电子型主体材料的电子迁移率来调节。例如，空穴型主体材料的空穴迁移率较高的情况下，则相应采用较大厚度的第一发光层，若空穴型主体材料的空穴迁移率较低，则相应采用较小厚度的第一发光层。第二发光层的厚度也可以采用类似方式调节。电子型主体材料的电子迁移率较高的情况下，相应采用较大厚度的第二发光层，若电子型主体材料的电子迁移率较低，则相应采用较小厚度的第二发光层。例如，第一发光层131和第二发光层132的厚度一般不同。可通过第一发光层131和第二发光层132的厚度控制来使得激子的复合中心在第一发光层131和第二发光层132的界面区域上，以保证激子的扩散范围在两层发光层区域内，避免激子扩散到其他层引起的淬灭，可省去电子阻挡层的使用。
例如，第一发光层131和第二发光层132总厚度约为20-40nm。
例如，该双层掺杂磷光发光器件可通过分别调节两层发光层的厚度控制载流子的传输，从而保证激子的扩散范围在两层发光层区域内，避免激子扩散到其他层引起的淬灭，省去电子阻挡层的使用。
例如，双层掺杂磷光发光器件还可包括空穴传输层11，且空穴型主体材料不同于空穴传输层11的空穴传输材料(第一发光层的空穴型主体材料与空穴传输层的空穴传输材料不同)。
若第一发光层131的空穴型主体材料不同于空穴传输层11的空穴传输材料，则可使得双层掺杂磷光发光器件利于寿命的优化，从而，双层掺杂磷光发光器件可以具有较长的使用寿命。
例如，双层掺杂磷光发光器件还可包括电子传输层12，且电子型主体材料不同于电子传输层12的电子传输材料(第二发光层的电子型主体材料与电子传输层的电子传输材料不同)。
若第二发光层132的电子型主体材料不同于电子传输层12的电子传输材 料，则可使得双层掺杂磷光发光器件利于寿命的优化，从而，双层掺杂磷光发光器件可以具有较长的使用寿命。
例如，第一发光层131的主体材料包括含咔唑基团的材料。例如，含咔唑基团的材料包括4,4'-N,N'-二咔唑联苯(CBP)、4,4',4”-三(咔唑-9-基)三苯胺(TCTA)和9,9’-(1,3-苯基)二-9H-咔唑(mCP)中的任意一种，但不限于此。
例如，空穴传输层11材料包括N,N’-双(1-萘基)-N,N’-二苯基-1,1’-二苯基-4,4’-二胺(NPB)、4,4′,4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺(m-MTDATA)和4,4-2-[N-(4-咔唑苯基)-N-苯基氨基]联苯(CPB)中的任意一种，但不限于此，厚度例如为20-70nm左右。
例如，第二发光层132的主体材料包括双(2-甲基-8-羟基喹啉)(4-l联苯氧基)铝(BAlq)、2,4,6-三(9H-咔唑-9-基)-1,3,5-三嗪(TRZ)和2,7-双(二苯基-氧化膦)-9,9-二甲基芴(PO6)中的任意一种，但不限于此。
例如，电子传输层12材料包括4,7-二苯基-1,10-邻二氮杂菲(BPhen)、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBI)和n型掺杂(n-doping)电子传输材料中的任意一种，但不限于此，厚度例如为10-30nm左右。n型掺杂电子传输材料例如包括2,9-二甲基-4,7-联苯-1,10-邻二氮杂菲(BCP):Li2CO3，8-羟基喹啉铝(Alq3):Mg，TPBI:Li等，但不限于此。
例如，第一发光层131和第二发光层132的客体材料为同一种磷光掺杂剂，从而可以发出单色光，可形成单色发光器件。
例如，第一发光层131和第二发光层132中磷光掺杂剂掺杂含量均小于10％(质量百分比)。
例如，磷光掺杂剂包括红色磷光材料和绿色磷光材料中的任意一种。
例如，红色磷光材料包括八乙基卟啉铂(PtOEP)、双(2-(2'-苯并噻吩基)吡啶-N,C3')(乙酰丙酮)合铱[(btp)2Ir(acac)]、三(二苯甲酰基甲烷)单(菲罗啉)铕(III)[Eu(dbm)3(Phen)]、三[1-苯基异喹啉-C2,N]铱(III)(Ir(piq)3)、二(1-苯基异喹啉)(乙酰丙酮)合铱(III)[Ir(piq)2(acac)]中的任意一种，但不限于此。
例如，绿色磷光材料包括三(2-苯基吡啶)合铱(Ir(ppy)3)、乙酰丙酮酸二(2-苯基吡啶)铱[Ir(ppy)2(acac)]、三(2-苯基吡啶)合铱(III)(Ir(mppy)3)、乙酰丙酮酸二(2-(4-氟苯基)-4-苯基吡啶)铱[Ir(FPP)2(acac)]、三(4-特丁基-2-苯基吡啶)合铱(Ir(Bu-ppy)3)中的任意一种，但不限于此。
例如，该双层掺杂磷光发光器件还可包括空穴注入层，阴极和阳极，还 可包括电子注入层等结构，该双层掺杂磷光发光器件的结构可为正常结构、倒置结构或透明结构。
图1示出了正常结构的双层掺杂磷光发光器件。双层掺杂磷光发光器件包括第一发光层131、第二发光层132、空穴传输层11和电子传输层12，各层材质可如前所述，还包括阴极14、阳极15和空穴注入层16。该结构中，阴极14可采用Mg:Ag合金(Mg-Ag合金)，厚度例如约为10-150nm(可根据器件类型，来选择适合的厚度)。阳极15可采用氧化铟锡(Indium tin oxide，ITO)，ITO阳极厚度例如约为10-150nm。空穴注入层16可采用金属氧化物MeO，例如MoO3，也可以采用p型掺杂的MeO(金属氧化物)-TPD(N,N’-双(3-甲基苯基)-N,N’–二苯基-1,1’–二苯基-4,4’–二胺):F4TCNQ(N,N,N',N’-四甲氧基苯基)-对二氨基联苯:2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌)或者m-MTDATA:F4TCNQ(4，4′，4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺:2,3,5,6-四氟-7,7',8,8'-四氰二甲基对苯醌)等，厚度例如约为1-30nm。
例如，一种正常结构的双层掺杂绿色磷光发光器件：阳极ITO150nm/m-MTDATA:F4TCNQ 30nm/m-MTDATA 60nm/CBP:Ir(ppy)37％24nm/BAlq:Ir(ppy)37％16nm/BPhen 10nm/Mg:Ag 100nm(阴极)。
例如，一种正常结构的双层掺杂红色磷光发光器件：阳极ITO150nm/m-MTDATA:F4TCNQ 30nm/m-MTDATA 60nm/CBP:Ir(piq)2(acac)7％24nm/BAlq:Ir(piq)2(acac)7％16nm/BPhen 10nm/Mg:Ag 100nm(阴极)。
图2示出了一种倒置结构的双层掺杂磷光发光器件示意图。双层掺杂磷光发光器件包括第一发光层131、第二发光层132、空穴传输层11、电子传输层12，各层材质可如前所述，在该实施例中，电子传输层12为n型掺杂的电子传输层，但不限于此。例如，该双层掺杂磷光发光器件还包括阴极14、阳极15和空穴注入层16。该结构中，阴极14可采用ITO，阳极15可采用Mg:Ag合金，空穴注入层16材料和厚度等可参见正常结构的双层掺杂磷光发光器件中所述，在此不再赘述。
例如，一种倒置结构的双层掺杂绿色磷光发光器件：阴极ITO 150nm/BCP:Li2CO310nm/BAlq:Ir(ppy)37％16nm/CBP:Ir(ppy)37％24nm/CPB40nm/MoO31nm/Mg:Ag 100nm(阳极)。
例如，一种倒置结构的红色磷光发光器件：阴极ITO 150nm/BCP:Li2CO3 10nm/BAlq:Ir(piq)2(acac)7％16nm/CBP:Ir(piq)2(acac)7％24nm/NPB40nm/MoO31nm/Mg:Ag 100nm(阳极)。
图3示出了一种透明结构的双层掺杂磷光发光器件示意图。双层掺杂磷光发光器件包括第一发光层131、第二发光层132、空穴传输层11和电子传输层12，还包括阴极14、阳极15、空穴注入层16和保护层17。阴极14可采用Mg:Ag合金或者ITO，阳极15可采用ITO，空穴注入层16、空穴传输层、电子传输层、以及第一发光层和第二发光层的主体材料和客体材料的材质及厚度均可如前所述。保护层17例如可采用金属氧化物或者高分子材料，其中，金属氧化物例如包括MoO3，高分子材料例如包括PEDOT:PSS[聚二氧乙基噻吩-聚苯乙烯磺酸]。当采用Mg:Ag合金作阴极时，可不设置保护层17。
本发明的实施例还提供一种双层掺杂磷光发光器件的制备方法，包括形成双层发光层13，其中，双层发光层13包括第一发光层131和第二发光层132，第一发光层131和第二发光层132均包括主体材料和客体材料，第一发光层131的主体材料为空穴型主体材料，第二发光层132的主体材料为电子型主体材料。
设置双层发光层，不仅可保证激子的扩散范围在两层发光层区域内，避免激子扩散到其他层引起的淬灭，省去电子阻挡层的使用。
例如，该方法中，第一发光层和第二发光层均可通过两源共蒸形成。制备方法简单。可以避免独立双主体掺杂中三源共蒸带来的因工艺掺杂比例的波动而导致的器件重复性能差的问题以及预混合的双主体掺杂中材料选择的限制。
例如，可通过空穴型主体材料的空穴迁移率和电子型主体材料的电子迁移率来确定第一发光层131和第二发光层132的厚度。
例如，可通过控制第一发光层和第二发光层的厚度，使激子的复合区域在第一发光层和第二发光层的界面区域上。
例如，该方法中，可通过分别调节两层发光层的厚度控制载流子的传输，从而保证激子的扩散范围在两层发光层区域内，避免激子扩散到其他层引起的淬灭，省去电子阻挡层的使用。
例如，该方法还包括形成空穴传输层11，其中，空穴型主体材料不同于空穴传输层11的空穴传输材料。
例如，空穴型主体材料不同于空穴传输层11的空穴传输材料，则可使得 双层掺杂磷光发光器件利于寿命的优化，从而，双层掺杂磷光发光器件可以具有较长的使用寿命。
例如，该方法还包括形成电子传输层12，其中，电子型主体材料不同于电子传输层12的电子传输材料。
例如，电子型主体材料不同于电子传输层12的电子传输材料，则可使得双层掺杂磷光发光器件利于寿命的优化，从而，双层掺杂磷光发光器件可以具有较长的使用寿命。
例如，该方法中，第一发光层131和第二发光层132主体材料和客体材料的选取、空穴传输层和电子传输层材料的选取、客体材料的掺杂量、第一发光层131和第二发光层132的厚度等均可参照上述双层掺杂磷光发光器件中所给出的内容。
通过上述方法，可制备出上述给出的各种双层掺杂磷光发光器件。
除非另作定义，此处使用的技术术语或者科学术语应当为本发明所属领域内具有一般技能的人士所理解的通常意义。本公开中使用的“第一”、“第二”以及类似的词语并不表示任何顺序、数量或者重要性，而只是用来区分不同的组成部分。同样，“包括”或者“包含”等类似的词语意指出现该词前面的元件或者物件涵盖出现在该词后面列举的元件或者物件及其等同，而不排除其他元件或者物件。
需要说明的是，本发明的实施例和附图中仅给出了与本发明实施例相关的内容和部件，未作描述的其他内容和部件可参见通常设计。本发明的实施例中磷光掺杂剂掺杂含量均指的是质量百分比。在本发明的实施例中所用各物质均为本领域常用物质，在该物质之前或之后的括号里给出了其缩写或者各缩写代表的物质的全称以方便理解。
本发明至少一实施例提供一种双层掺杂磷光发光器件及其制备方法，该双层掺杂磷光发光器件包括双层发光层，其中，双层发光层包括第一发光层和第二发光层，第一发光层和第二发光层均包括主体材料和客体材料，第一发光层的主体材料为空穴型主体材料，第二发光层的主体材料为电子型主体材料。该双层掺杂磷光发光器件可以避免独立双主体掺杂中三源共蒸带来的因工艺掺杂比例的波动而导致的器件重复性能差的问题以及预混合的双主体掺杂中材料选择的限制。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限 于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应以所述权利要求的保护范围为准。
本专利申请要求于2015年5月26日递交的中国专利申请第201510276057.9号的优先权，在此全文引用上述中国专利申请公开的内容以作为本申请的一部分。

Claims (20)

  1. 一种双层掺杂磷光发光器件，包括双层发光层，其中，所述双层发光层包括第一发光层和第二发光层，所述第一发光层和第二发光层均包括主体材料和客体材料，所述第一发光层的主体材料为空穴型主体材料，所述第二发光层的主体材料为电子型主体材料。
  2. 根据权利要求1所述的双层掺杂磷光发光器件，其中，所述第一发光层的厚度对应于所述空穴型主体材料的空穴迁移率，所述第二发光层的厚度对应于所述电子型主体材料的电子迁移率。
  3. 根据权利要求1或2所述的双层掺杂磷光发光器件，其中，所述第一发光层和所述第二发光层的厚度不同。
  4. 根据权利要求1-3任一项所述的双层掺杂磷光发光器件，其中，所述第一发光层和第二发光层总厚度为20-40nm。
  5. 根据权利要求1-4任一项所述的双层掺杂磷光发光器件，还包括空穴传输层，其中，所述空穴型主体材料不同于空穴传输层的空穴传输材料。
  6. 根据权利要求5所述的双层掺杂磷光发光器件，其中，所述第一发光层的主体材料包括含咔唑基团的材料，所述含咔唑基团的材料包括4,4'-N,N'-二咔唑联苯(CBP)、4,4',4”-三(咔唑-9-基)三苯胺(TCTA)和9,9’-(1,3-苯基)二-9H-咔唑(mCP)中的任意一种，所述空穴传输层材料包括N,N’-双(1-萘基)-N,N’-二苯基-1,1’-二苯基-4,4’-二胺(NPB)、4,4′,4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺(m-MTDATA)和4,4-2-[N-(4-咔唑苯基)-N-苯基氨基]联苯(CPB)中的任意一种。
  7. 根据权利要求1-6任一项所述的双层掺杂磷光发光器件，还包括电子传输层，其中，所述电子型主体材料不同于所述电子传输层的电子传输材料。
  8. 根据权利要求7所述的双层掺杂磷光发光器件，其中，所述第二发光层的主体材料包括双(2-甲基-8-羟基喹啉)(4-l联苯氧基)铝(BAlq)、2,4,6-三(9H-咔唑-9-基)-1,3,5-三嗪(TRZ)和2,7-双(二苯基-氧化膦)-9,9-二甲基芴(PO6)中的任意一种，所述电子传输层材料包括4,7-二苯基-1,10-邻二氮杂菲(BPhen)、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBI)和n型掺杂电子传输材料中的任意一种。
  9. 根据权利要求1-8任一项所述的双层掺杂磷光发光器件，其中，所述 第一发光层和第二发光层的客体材料为同一种磷光掺杂剂，所述磷光掺杂剂包括红色磷光材料和绿色磷光材料中的任意一种。
  10. 根据权利要求9所述的双层掺杂磷光发光器件，其中，所述红色磷光材料包括八乙基卟啉铂(PtOEP)、双(2-(2'-苯并噻吩基)吡啶-N,C3')(乙酰丙酮)合铱[(btp)2Ir(acac)]、三(二苯甲酰基甲烷)单(菲罗啉)铕(III)[Eu(dbm)3(Phen)]、三[1-苯基异喹啉-C2,N]铱(III)(Ir(piq)3)、二(1-苯基异喹啉)(乙酰丙酮)合铱(III)[Ir(piq)2(acac)]中的任意一种；
    所述绿色磷光材料包括三(2-苯基吡啶)合铱(Ir(ppy)3)、乙酰丙酮酸二(2-苯基吡啶)铱[Ir(ppy)2(acac)]、三(2-苯基吡啶)合铱(III)(Ir(mppy)3)、乙酰丙酮酸二(2-(4-氟苯基)-4-苯基吡啶)铱[Ir(FPP)2(acac)]、三(4-特丁基-2-苯基吡啶)合铱(Ir(Bu-ppy)3)中的任意一种。
  11. 一种双层掺杂磷光发光器件的制备方法，包括形成双层发光层，其中，所述形成双层发光层包括形成第一发光层和形成第二发光层，所述第一发光层和第二发光层均包括主体材料和客体材料，所述第一发光层的主体材料为空穴型主体材料，所述第二发光层的主体材料为电子型主体材料。
  12. 根据权利要求11所述的双层掺杂磷光发光器件的制备方法，其中，所述第一发光层和第二发光层均通过两源共蒸形成。
  13. 根据权利要求11或12所述的双层掺杂磷光发光器件的制备方法，其中，通过所述空穴型主体材料的空穴迁移率和所述电子型主体材料的电子迁移率来确定所述第一发光层和所述第二发光层的厚度。
  14. 根据权利要求11-13任一项所述的双层掺杂磷光发光器件的制备方法，其中，通过控制所述第一发光层和第二发光层的厚度，使激子的复合区域在所述第一发光层和所述第二发光层的界面区域上。
  15. 根据权利要求11-14任一项所述的双层掺杂磷光发光器件的制备方法，还包括形成空穴传输层，其中，所述空穴型主体材料不同于空穴传输层的空穴传输材料。
  16. 根据权利要求15所述的双层掺杂磷光发光器件的制备方法，其中，所述第一发光层的主体材料包括含咔唑基团的材料，所述含咔唑基团的材料包括4,4'-N,N'-二咔唑联苯(CBP)、4,4',4”-三(咔唑-9-基)三苯胺(TCTA)和9,9’-(1,3-苯基)二-9H-咔唑(mCP)中的任意一种，所述空穴传输层材料包括N,N’-双(1-萘基)-N,N’-二苯基-1,1’-二苯基-4,4’-二胺(NPB)、4,4′,4″-三(N-3- 甲基苯基-N-苯基氨基)三苯胺(m-MTDATA)和4,4-2-[N-(4-咔唑苯基)-N-苯基氨基]联苯(CPB)中的任意一种。
  17. 根据权利要求11-16任一项所述的双层掺杂磷光发光器件的制备方法，还包括形成电子传输层，其中，所述电子型主体材料不同于所述电子传输层的电子传输材料。
  18. 根据权利要求17所述的双层掺杂磷光发光器件的制备方法，其中，所述第二发光层的主体材料包括双(2-甲基-8-羟基喹啉)(4-l联苯氧基)铝(BAlq)、2,4,6-三(9H-咔唑-9-基)-1,3,5-三嗪(TRZ)和2,7-双(二苯基-氧化膦)-9,9-二甲基芴(PO6)中的任意一种，所述电子传输层材料包括4,7-二苯基-1,10-邻二氮杂菲(BPhen)、1,3,5-三(1-苯基-1H-苯并咪唑-2-基)苯(TPBI)和n型掺杂电子传输材料中的任意一种。
  19. 根据权利要求11-18任一项所述的双层掺杂磷光发光器件的制备方法，其中，所述第一发光层和第二发光层的客体材料为同一种磷光掺杂剂，所述磷光掺杂剂包括红色磷光材料和绿色磷光材料中的任意一种。
  20. 根据权利要求19所述的双层掺杂磷光发光器件的制备方法，其中，
    所述红色磷光材料包括八乙基卟啉铂(PtOEP)、双(2-(2'-苯并噻吩基)吡啶-N,C3')(乙酰丙酮)合铱[(btp)2Ir(acac)]、三(二苯甲酰基甲烷)单(菲罗啉)铕(III)[Eu(dbm)3(Phen)]、三[1-苯基异喹啉-C2,N]铱(III)(Ir(piq)3)、二(1-苯基异喹啉)(乙酰丙酮)合铱(III)[Ir(piq)2(acac)]中的任意一种；
    所述绿色磷光材料包括三(2-苯基吡啶)合铱(Ir(ppy)3)、乙酰丙酮酸二(2-苯基吡啶)铱[Ir(ppy)2(acac)]、三(2-苯基吡啶)合铱(III)(Ir(mppy)3)、乙酰丙酮酸二(2-(4-氟苯基)-4-苯基吡啶)铱[Ir(FPP)2(acac)]、三(4-特丁基-2-苯基吡啶)合铱(Ir(Bu-ppy)3)中的任意一种。
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