CN104466012A - Organic light emitting device and preparation method thereof - Google Patents
Organic light emitting device and preparation method thereof Download PDFInfo
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- CN104466012A CN104466012A CN201310429687.6A CN201310429687A CN104466012A CN 104466012 A CN104466012 A CN 104466012A CN 201310429687 A CN201310429687 A CN 201310429687A CN 104466012 A CN104466012 A CN 104466012A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000011521 glass Substances 0.000 claims abstract description 52
- 238000002347 injection Methods 0.000 claims abstract description 48
- 239000007924 injection Substances 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- 230000005525 hole transport Effects 0.000 claims abstract description 17
- 239000005749 Copper compound Substances 0.000 claims abstract description 14
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 14
- 238000001704 evaporation Methods 0.000 claims description 36
- 230000008020 evaporation Effects 0.000 claims description 33
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 31
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 24
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 22
- 238000005566 electron beam evaporation Methods 0.000 claims description 21
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 10
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 10
- 230000017525 heat dissipation Effects 0.000 claims description 10
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 8
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 8
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 7
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 7
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 6
- 229940112669 cuprous oxide Drugs 0.000 claims description 6
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims description 6
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 6
- 229960004643 cupric oxide Drugs 0.000 claims description 5
- JAONJTDQXUSBGG-UHFFFAOYSA-N dialuminum;dizinc;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Zn+2].[Zn+2] JAONJTDQXUSBGG-UHFFFAOYSA-N 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- AYTVLULEEPNWAX-UHFFFAOYSA-N cesium;azide Chemical compound [Cs+].[N-]=[N+]=[N-] AYTVLULEEPNWAX-UHFFFAOYSA-N 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 claims description 3
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical group C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 claims description 3
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- MQCHTHJRANYSEJ-UHFFFAOYSA-N n-[(2-chlorophenyl)methyl]-1-(3-methylphenyl)benzimidazole-5-carboxamide Chemical compound CC1=CC=CC(N2C3=CC=C(C=C3N=C2)C(=O)NCC=2C(=CC=CC=2)Cl)=C1 MQCHTHJRANYSEJ-UHFFFAOYSA-N 0.000 claims description 3
- QWODREODAXFISP-UHFFFAOYSA-N n-[4-(4-anilinophenyl)phenyl]-n-phenylnaphthalen-1-amine Chemical compound C=1C=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=CC=1NC1=CC=CC=C1 QWODREODAXFISP-UHFFFAOYSA-N 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 claims description 3
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 claims description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 7
- 238000000149 argon plasma sintering Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 3
- ZVFQEOPUXVPSLB-UHFFFAOYSA-N 3-(4-tert-butylphenyl)-4-phenyl-5-(4-phenylphenyl)-1,2,4-triazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C(N1C=2C=CC=CC=2)=NN=C1C1=CC=C(C=2C=CC=CC=2)C=C1 ZVFQEOPUXVPSLB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- HXWWMGJBPGRWRS-CMDGGOBGSA-N 4- -2-tert-butyl-6- -4h-pyran Chemical compound O1C(C(C)(C)C)=CC(=C(C#N)C#N)C=C1\C=C\C1=CC(C(CCN2CCC3(C)C)(C)C)=C2C3=C1 HXWWMGJBPGRWRS-CMDGGOBGSA-N 0.000 description 2
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 2
- CRHRWHRNQKPUPO-UHFFFAOYSA-N 4-n-naphthalen-1-yl-1-n,1-n-bis[4-(n-naphthalen-1-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 CRHRWHRNQKPUPO-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- 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
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
-
- 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
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an organic light emitting device and a preparation method thereof. The organic light emitting device is of a layered structure comprising a glass substrate, an anode layer, a scattering layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer, all of which are sequentially stacked. The scattering layer includes a three-element doped layer which contains a metal oxide with hole injection ability, a copper compound and a hole doped object material. The scattering layer of the organic light emitting device of the invention improves the hole injection ability, the hole transport rate and light scattering, and thus improves the light extraction efficiency.
Description
Technical Field
The invention relates to the field of photoelectronic devices, in particular to an organic electroluminescent device. The invention also relates to a preparation method of the organic electroluminescent device.
Background
In 1987, c.w.tang and VanSlyke of Eastman Kodak company, usa, reported a breakthrough development in organic electroluminescence studies. A double-layer organic electroluminescent device (OLED) with high brightness and high efficiency is prepared by using an ultrathin film technology. The brightness reaches 1000cd/m under 10V2The luminous efficiency is 1.51lm/W, and the lifetime is longer than 100 hours.
In the existing light-emitting device, only about 18% of light inside the device can be emitted to the outside, while other parts can be consumed outside the device in other forms, and the difference of refractive indexes (such as the difference of refractive indexes between glass and ITO) exists between interfaces. Specifically, when the refractive index of glass of the conventional light emitting device is 1.5 and the refractive index of ITO is 1.8, light reaches the glass from the ITO, and total reflection occurs, which causes loss of total reflection, resulting in low overall light extraction performance.
Disclosure of Invention
The present invention is directed to solve the problems and disadvantages of the prior art, and provides an organic electroluminescent device and a method for fabricating the same to improve the light extraction efficiency of the organic electroluminescent device.
The technical scheme provided by the invention aiming at the technical problems is as follows:
an organic electroluminescent device, the organic electroluminescent device having a layered structure, the layered structure comprising: the light-emitting diode comprises a glass substrate, an anode layer, a scattering layer, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode layer which are sequentially laminated; the scattering layer comprises a ternary doping layer; the material of the ternary doped layer comprises metal oxide with hole injection capability, a copper compound and a hole-doped guest material;
the metal oxide is molybdenum trioxide (MoO)3) Tungsten trioxide (WO)3) Or vanadium pentoxide (V)2O5）；
The copper compound is cuprous iodide (CuI) or cuprous oxide (Cu)2O), copper phthalocyanine (CuPc), or copper oxide (CuO);
the hole-doped guest materials are 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyano-p-quinodimethane F4-TCNQ, 4, 4, 4-tris (naphthyl-1-phenyl-ammonium) triphenylamine (1T-NATA) and dinaphthyl-N, N '-diphenyl-4, 4' -biphenyldiamine (2T-NATA).
Further, the mass ratio of the metal oxide to the copper compound to the hole-doped guest material is 10:5:1 to 40:10: 1.
Further, the glass substrate has a refractive index of 1.8 or more and a visible light transmittance of 90% or more.
Further, the thickness of the ternary doping layer is 50-300 nm.
Further, the anode layer is made of Indium Tin Oxide (ITO), aluminum zinc oxide (ATO) or Indium Zinc Oxide (IZO);
the hole injection layer is made of molybdenum trioxide (MoO)3) Tungsten trioxide (WO)3) Or vanadium pentoxide (V)2O5）；
The material of the hole transport layer is 1, 1-bis [4- [ N, N ' -bis (p-tolyl) amino ] phenyl ] cyclohexane (TAPC), 4', 4' ' -tris (carbazol-9-yl) triphenylamine (TCTA) or N, N ' - (1-naphthyl) -N, N ' -diphenyl-4, 4' -biphenyldiamine (NPB);
the material of the luminescent layer is 4- (dinitrile methyl) -2-butyl-6- (1, 1, 7, 7-tetramethyl jirimycin-9-vinyl) -4H-pyran (DCJTB), 9, 10-di-beta-naphthylene Anthracene (ADN), 4 '-bis (9-ethyl-3-carbazole vinyl) -1, 1' -biphenyl (BCzVBi) or 8-hydroxyquinoline aluminum (Alq)3）；
The material of the electron transport layer is 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 1, 2, 4-triazole derivative (such as TAZ) or N-aryl benzimidazole (TPBI);
the electron injection layer is made of cesium carbonate (Cs)2CO3) Cesium fluoride (CsF), cesium azide (CsN)3) Or lithium fluoride (LiF).
The cathode layer is made of silver (Ag), aluminum (Al), platinum (Pt) or gold (Au).
The invention also provides a preparation method of the organic electroluminescent device, which comprises the following steps:
(a) preparing an anode layer on a glass substrate by a magnetron sputtering device;
(b) preparing a ternary doping layer on the anode layer prepared in the step (a) by using an electron beam evaporation device so as to obtain the heat dissipation layer; wherein,
the material of the ternary doped layer comprises metal oxide with hole injection capability, a copper compound and a hole-doped guest material;
the metal oxide is molybdenum trioxide, tungsten trioxide or vanadium pentoxide;
the copper compound is cuprous iodide, cuprous oxide, copper phthalocyanine or cupric oxide;
the hole-doped guest material is 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyano-p-phenylenediamine dimethane, 4, 4, 4-tri (naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, 4' -biphenyldiamine;
(c) and (c) sequentially evaporating a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer on the scattering layer prepared in the step (b), so as to obtain the organic electroluminescent device.
Further, in the step (a), the accelerating voltage of the magnetron sputtering equipment is 300-800V, the magnetic field is 50-200G, and the power density is 1-40W/cm2。
Further, in the step (b), the doping mass ratio of the metal oxide having hole injection capability, the copper compound and the hole-doped guest material is 10:5:1 to 40:10: 1.
Further, in the step (b), the electron beam evaporation energy density of the electron beam evaporation equipment is 10 to l00W/cm2The thickness of the ternary doping layer is 50-300 nm.
Further, in the step (c), the evaporation rate of the hole transport layer, the luminescent layer and the electron transport layer is 0.1-1 nm/s, and the evaporation rate of the cathode layer is 1-10 nm/s.
The organic electroluminescent device adopts a glass substrate with the refractive index of more than 1.8 and the visible light transmittance of more than 90 percent, and a scattering layer is prepared on the glass substrate. The wavelength of the visible light is preferably 400 nm. The properties of the components of the scattering layer are as follows: the metal oxide with the hole injection capability of the scattering layer has a wider energy gap, the HOMO energy level of the metal oxide is very low, the hole injection capability can be improved, the LUMO energy level is very high, the transmission of electrons can be blocked, the phenomenon that the electrons reach an anode and are compounded with the holes to generate leakage current is avoided, meanwhile, the glass transition temperature is very low (below 50 ℃), the metal oxide is very easy to crystallize, the crystallized crystal structure has a scattering effect on light, the scattering of light is enhanced, and the light extraction efficiency is improved; the metal oxide nano-particle size of the scattering layer is larger, so that the scattering of light can be improved, and light emitted to two sides returns to the middle; the copper compound of the scattering layer has a lower HOMO energy level, so that hole injection is facilitated, the hole injection capability is further improved, the atomic radius is larger, photon scattering is facilitated, the incident angle is changed after repeated back and forth reflection is carried out in the crystal, the hole doping material and the metal oxide can form p doping, the hole transmission rate is improved, and the light extraction efficiency is improved. The HOMO energy level is a term derived from the front-line orbital theory, and means an orbital having the highest energy level of an occupied electron, and is a representation of the ability to donate an electron.
In summary, compared with the prior art, the organic electroluminescent device and the preparation method thereof of the present invention have the following advantages: the scattering layer of the organic electroluminescent device improves the injection capability of the holes, the transmission rate of the holes and the light scattering, thereby being beneficial to improving the light extraction efficiency.
Drawings
Fig. 1 is a schematic structural view of an organic electroluminescent device of embodiment 1 of the present invention.
Fig. 2 is a graph of current density versus current efficiency for the organic electroluminescent device of example 1 and the comparative example.
Detailed Description
The present invention will be further described in detail with reference to the following examples.
Example 1
As shown in fig. 1, the organic electroluminescent device in this embodiment has a layered structure, and each layer sequentially includes:
a glass substrate 101, an anode layer 102, a ternary doping layer 103, a hole injection layer 104, a hole transport layer 105, a light emitting layer 106, an electron transport layer 107, an electron injection layer 108, and a cathode layer 109. The ternary doping layer 103 constitutes the heat dissipation layer. The organic electroluminescent device is structurally characterized in that a glass substrate ITO/MoO3:Cu2O:F4-TCNQ/WO3[ the term "/" denotes a layered structure, colon ": "means mutually doped. )
The organic electroluminescent device is prepared by the following steps in sequence:
pretreatment of (I) plating film
The glass substrate 101 with the glass brand number of N-LASF44 is taken out, washed clean by distilled water and ethanol and then soaked in isopropanol for one night.
(II) preparation of anode layer
Placing the glass substrate 101 prepared in the step (I) under a magnetron sputtering device, and setting the process parameters of the magnetron sputtering device to an accelerating voltage of 700V, a magnetic field of 120G and 250W/cm2The anode layer 102 is prepared on the glass substrate 101 by using a magnetron sputtering device, and the anode layer 102 is made of indium tin oxide and has a thickness of 150 nm.
Preparation of the (III) Scattering layer
Placing the glass substrate 101 prepared in the step (II) under electron beam evaporation preparation, and setting the electron beam evaporation energy density of the electron beam evaporation preparation to be 30W/cm2The target material is molybdenum trioxide, cuprous oxide and 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyano-p-phenylenediquinone dimethane, the ternary doping layer 103 is prepared by evaporation on the anode layer 102 by electron beam evaporation so that the thickness of the ternary doping layer 103 is 250nm, and the doping amount ratio of molybdenum trioxide, cuprous oxide and 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyano-phenylenediquinone dimethane in the ternary doping layer 103 is 20:6:1, thereby preparing the heat dissipation layer.
(IV) preparation of organic electroluminescent device
Transposing the glass substrate 101 prepared in the step (three) under thermal resistance evaporation preparation, and setting the technological parameters of the thermal resistance evaporation preparation to be 0.2nm/s evaporation rate and 8 multiplied by 10-4Pa, using thermal resistance evaporation to sequentially evaporate a hole injection layer 104 which is made of tungsten trioxide and has the thickness of 30nm and is made of N, N' - (1-naphthyl) -N on the ternary doping layer 103, a hole-transporting layer 105 of N '-diphenyl-4, 4' -biphenyldiamine with a thickness of 50nm, a light-emitting layer 106 of 4, 4 '-bis (9-ethyl-3-carbazolevinyl) -1, 1' -biphenyl with a thickness of 16nm, an electron-transporting layer 107 of 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-triazole with a thickness of 210nm, an electron-injecting layer 108 of cesium fluoride with a thickness of 1 nm; then, the evaporation rate of the thermal resistance evaporation preparation is adjusted to 2nm/s, and the cathode layer 109 which is made of silver and has the thickness of 160nm is prepared on the electron injection layer 108 by using the thermal resistance evaporation, so that the required electroluminescent device is obtained.
Fig. 2 is a graph of the lumen efficiency of the organic electroluminescent device of example 1 and a general device as a function of current density. The structure of the general device is glass substrate/ITO/WO3the/NPB/BCzVBi/TAZ/CsF/Ag. In FIG. 2, the abscissa represents the magnitude of the current density and the ordinate represents the lumen efficiencyCurve 1 is the current density versus lumen efficiency curve for the organic electroluminescent device of example 1, and curve 2 is the current density versus lumen efficiency curve for the comparative device. As can be seen from FIG. 2, the luminous efficiency of example 1 is greater than that of the comparative example, the maximum luminous efficiency is 5.0lm/W, while that of the comparative example is only 3.7lm/W, and the luminous efficiency of the comparative example decreases rapidly with the increase of the current density, which shows that the scattering layer prepared by the invention can improve the injection capability of holes, improve the scattering of light, return the light emitted to the two sides to the middle, form p doping, improve the transmission rate of holes, and thus is beneficial to improving the light extraction efficiency.
Example 2
The organic electroluminescent device in this embodiment has a layered structure, and each layer sequentially includes: the organic electroluminescent device comprises a glass substrate, an anode layer, a ternary doping layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer.
And the ternary doping layer form the heat dissipation layer. The organic electroluminescent device has a structure of glass substrate/IZO/WO3:CuI:1T-NATA/MoO3/TCTA/ADN/Bphen/CsN3Al, where diagonal "/" denotes a layered structure, colon ": "means mutually doped. The organic electroluminescent device is prepared by the following steps in sequence:
pretreatment of (I) plating film
Taking out the glass substrate with the glass brand of N-LAF36, washing the glass substrate with distilled water and ethanol, and soaking the glass substrate in isopropanol for one night.
(II) preparation of anode layer
Placing the glass substrate prepared in the step (I) under a magnetron sputtering device, and setting the process parameters of the magnetron sputtering device to 300V of accelerating voltage, 50G of magnetic field and 40W/cm2Power density of (2) using magnetron sputteringThe anode layer was made of Indium Zinc Oxide (IZO) and 80nm thick on a glass substrate.
Preparation of the (III) Scattering layer
Placing the glass substrate 101 prepared in the step (II) under electron beam evaporation preparation, and setting the electron beam evaporation energy density of the electron beam evaporation preparation to 100W/cm2The target material was tungsten trioxide, cuprous iodide, and 4, 4, 4-tris (naphthyl-1-phenyl-ammonium) triphenylamine, and a ternary doping layer 103 was vapor-deposited on the anode layer 102 by electron beam vapor deposition so that the thickness of the ternary doping layer 103 was 300nm, and the doping mass ratio of tungsten trioxide, cuprous iodide, and 4, 4, 4-tris (naphthyl-1-phenyl-ammonium) triphenylamine in the ternary doping layer 103 was 10:5:1, thereby producing a heat dissipation layer.
(IV) preparation of organic electroluminescent device
Placing the glass substrate prepared in the step (three) under thermal resistance evaporation preparation, and setting the technological parameters of the thermal resistance evaporation preparation to be the evaporation rate of 1nm/s and 2 multiplied by 10-3A working pressure Pa, preparing a hole injection layer which is made of molybdenum trioxide and has the thickness of 40nm, a hole transport layer which is made of 4, 4', 4' ' -tri (carbazole-9-yl) triphenylamine and has the thickness of 45nm, a light emitting layer which is made of 9, 10-di-beta-naphthylene anthracene and has the thickness of 8nm, an electron transport layer which is made of 4, 7-diphenyl-1, 10-phenanthroline and has the thickness of 65nm, and an electron injection layer which is made of cesium azide and has the thickness of 10nm on the ternary doping layer by thermal resistance evaporation; and then regulating the evaporation rate of thermal resistance evaporation preparation to 10nm/s, and preparing a cathode layer which is made of aluminum and has the thickness of 80nm on the electron injection layer by using thermal resistance evaporation, thereby obtaining the required electroluminescent device.
Example 3
The organic electroluminescent device in this embodiment has a layered structure, and each layer sequentially includes:
glass substrate and anodeThe organic electroluminescent device comprises a layer, a ternary doping layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer. And the ternary doping layer form the heat dissipation layer. The organic electroluminescent device has a structure of glass substrate/AZO/V2O5:CuPc:2T-NATA/V2O5/TAPC/Alq3TPBi/LiF/Al, wherein the diagonal "/" indicates a layered structure, colon ": "means mutually doped. The organic electroluminescent device is prepared by the following steps in sequence:
pretreatment of (I) plating film
Taking out the glass substrate with the glass brand number of N-LASF31A, washing the glass substrate with distilled water and ethanol, and soaking the glass substrate in isopropanol for one night.
(II) preparation of anode layer
Placing the glass substrate prepared in the step (I) under a magnetron sputtering device, and setting the process parameters of the magnetron sputtering device to 800V of accelerating voltage, 200G of magnetic field and 1W/cm2Using the magnetron sputtering equipment to prepare an anode layer which is made of Aluminum Zinc Oxide (AZO) and has a thickness of 300nm on the glass substrate.
Preparation of the (III) Scattering layer
Placing the glass substrate 101 prepared in the step (II) under electron beam evaporation preparation, and setting the electron beam evaporation energy density of the electron beam evaporation preparation to l0W/cm2The target material is set to be vanadium pentoxide, copper phthalocyanine and dinaphthyl-N, N '-diphenyl-4, 4' -biphenyldiamine, the ternary doping layer 103 is prepared on the anode layer 102 by evaporation through electron beam evaporation, the thickness of the ternary doping layer 103 is 50nm, and the doping mass ratio of the vanadium pentoxide, the copper phthalocyanine and the dinaphthyl-N, N '-diphenyl-4, 4' -biphenyldiamine in the ternary doping layer 103 is 40:10:1, so that the heat dissipation layer is prepared.
(IV) preparation of organic electroluminescent device
The third stepThe prepared glass substrate is placed under thermal resistance evaporation preparation, and the technological parameters of the thermal resistance evaporation preparation are set to be 0.1nm/s evaporation rate and 5 multiplied by 10-5Pa, using thermal resistance evaporation to prepare a hole injection layer with the material of vanadium pentoxide and the thickness of 20nm on the ternary doping layer on the glass substrate, and the material of 1, 1-bis [4- [ N, N' -bis (p-tolyl) amino]Phenyl radical]A hole transport layer of cyclohexane with a thickness of 60nm, a luminescent layer of 8-hydroxyquinoline aluminum with a thickness of 40nm, an electron transport layer of N-arylbenzimidazole with a thickness of 200nm, and an electron injection layer of lithium fluoride with a thickness of 0.5 nm; and then regulating the evaporation rate of thermal resistance evaporation preparation to 1nm/s, and preparing a cathode layer which is made of gold and has the thickness of 100nm on the electron injection layer by using the thermal resistance evaporation preparation, thereby obtaining the required electroluminescent device.
Example 4
The organic electroluminescent device in this embodiment has a layered structure, and each layer sequentially includes:
the organic electroluminescent device comprises a glass substrate, an anode layer, a ternary doping layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer. And the ternary doping layer form the heat dissipation layer. The organic electroluminescent device has a structure of glass substrate ITO/WO3:CuO:F4-TCNQ/WO3/NPB/DCJTB/Bphen/Cs2CO3Pt, where diagonal "/" denotes a layered structure, colon ": "means mutually doped. The organic electroluminescent device is prepared by the following steps in sequence:
pretreatment of (I) plating film
Taking out the glass substrate with the glass brand number of N-LASF41A, washing the glass substrate with distilled water and ethanol, and soaking the glass substrate in isopropanol for one night.
(II) preparation of anode layer
The glass base prepared by the step (one)Setting the technological parameters of the magnetron sputtering equipment to be an accelerating voltage of 600V, a magnetic field of 100G and a magnetic field of 30W/cm2The anode layer was prepared on a glass substrate using a magnetron sputtering apparatus with a material of Indium Tin Oxide (ITO) and a thickness of 180 nm.
Preparation of the (III) Scattering layer
Placing the glass substrate 101 prepared in the step (II) under electron beam evaporation preparation, and setting the electron beam evaporation energy density of the electron beam evaporation preparation to be 25W/cm2The target material was tungsten trioxide, copper oxide, and 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyano-p-quinodimethane, and a ternary doping layer 103 was vapor-deposited on the anode layer 102 using electron beam evaporation so that the thickness of the ternary doping layer 103 was 200nm, and the doping mass ratio of tungsten trioxide, copper oxide, and 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyano-p-quinodimethane in the ternary doping layer 103 was 30:10:1, thereby producing a heat dissipation layer.
(IV) preparation of organic electroluminescent device
Placing the glass substrate prepared in the step (three) under thermal resistance evaporation preparation, and setting the technological parameters of the thermal resistance evaporation preparation to be 0.5nm/s evaporation rate and 2 multiplied by 10-4Pa, preparing a hole injection layer which is formed by sequentially evaporating tungsten trioxide and has the thickness of 80nm, a hole transport layer which is formed by N, N ' - (1-naphthyl) -N, N ' -diphenyl-4, 4' -biphenyldiamine and has the thickness of 60nm, a light emitting layer which is formed by 4- (dinitrile methyl) -2-butyl-6- (1, 1, 7, 7-tetramethyl-lingeridine-9-vinyl) -4H-pyran and has the thickness of 10nm, an electron transport layer which is formed by 4, 7-diphenyl-1, 10-phenanthroline and has the thickness of 35nm, and an electron injection layer which is formed by cesium carbonate and has the thickness of 3 nm; and then regulating the evaporation rate of thermal resistance evaporation preparation to 6nm/s, and preparing a cathode layer which is made of platinum and has the thickness of 250nm on the electron injection layer by using thermal resistance evaporation, thereby obtaining the required electroluminescent device.
Compared with the prior art, the scattering layer of the organic light-emitting device improves the injection capability of the holes, the transmission rate of the holes and the light scattering, thereby being beneficial to improving the light-emitting efficiency.
The above test and preparation equipment is a high vacuum coating system (Shenyang scientific instruments development center, Ltd.), a USB4000 fiber optic spectrometer of Ocean optical Ocean Optics for testing electroluminescence spectrum, Keithley2400 of Gibbery corporation for testing electrical properties, and a CS-100A colorimeter of Konika Mentada corporation for testing brightness and chromaticity.
The above-mentioned embodiments are merely preferred examples of the present invention, and not intended to limit the present invention, and those skilled in the art can easily make various changes and modifications according to the main concept and spirit of the present invention, so that the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. An organic electroluminescent device, the organic electroluminescent device having a layered structure, wherein the layered structure comprises: the light-emitting diode comprises a glass substrate, an anode layer, a scattering layer, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode layer which are sequentially laminated; the scattering layer comprises a ternary doping layer; the material of the ternary doped layer comprises metal oxide with hole injection capability, a copper compound and a hole-doped guest material;
the metal oxide is molybdenum trioxide, tungsten trioxide or vanadium pentoxide;
the copper compound is cuprous iodide, cuprous oxide, copper phthalocyanine or cupric oxide;
the hole-doped guest materials are 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyano-p-phenylenediquinone dimethane, 4, 4, 4-tris (naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, 4' -biphenyldiamine.
2. The organic electroluminescent device according to claim 1, wherein the mass ratio of the metal oxide to the copper compound to the hole-doped guest material is 10:5:1 to 40:10: 1.
3. The organic electroluminescent device according to claim 1, wherein the glass substrate has a refractive index of 1.8 or more and a visible light transmittance of 90% or more.
4. The organic electroluminescent device according to claim 1, wherein the thickness of the ternary doping layer is 50 to 300 nm.
5. The organic electroluminescent device according to claim 1,
the anode layer is made of indium tin oxide, aluminum zinc oxide or indium zinc oxide;
the hole injection layer is made of molybdenum trioxide, tungsten trioxide or vanadium pentoxide;
the material of the hole transport layer is 1, 1-bis [4- [ N, N ' -di (p-tolyl) amino ] phenyl ] cyclohexane, 4', 4' ' -tris (carbazol-9-yl) triphenylamine or N, N ' - (1-naphthyl) -N, N ' -diphenyl-4, 4' -biphenyldiamine;
the material of the light-emitting layer is 4- (dinitrile methyl) -2-butyl-6- (1, 1, 7, 7-tetramethyl-cyclolidine-9-vinyl) -4H-pyran, 9, 10-di-beta-naphthylene anthracene, 4 '-bis (9-ethyl-3-carbazole vinyl) -1, 1' -biphenyl or 8-hydroxyquinoline aluminum;
the electron transport layer is made of 4, 7-diphenyl-1, 10-phenanthroline, 1, 2, 4-triazole derivatives or N-aryl benzimidazole;
the electron injection layer is made of cesium carbonate, cesium fluoride, cesium azide or lithium fluoride.
6. A preparation method of an organic electroluminescent device is characterized by comprising the following steps:
(a) preparing an anode layer on a glass substrate by a magnetron sputtering device;
(b) preparing a ternary doping layer on the anode layer prepared in the step (a) by using an electron beam evaporation device so as to obtain the heat dissipation layer; wherein,
the material of the ternary doped layer comprises metal oxide with hole injection capability, a copper compound and a hole-doped guest material;
the metal oxide is molybdenum trioxide, tungsten trioxide or vanadium pentoxide;
the copper compound is cuprous iodide, cuprous oxide, copper phthalocyanine or cupric oxide;
the hole-doped guest material is 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyano-p-phenylenediamine dimethane, 4, 4, 4-tri (naphthyl-1-phenyl-ammonium) triphenylamine and dinaphthyl-N, N '-diphenyl-4, 4' -biphenyldiamine;
(c) and (c) sequentially evaporating a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode layer on the scattering layer prepared in the step (b), so as to obtain the organic electroluminescent device.
7. The method according to claim 6, wherein the magnetron sputtering apparatus in the step (a) has an acceleration voltage of 300 to 800V, a magnetic field of 50 to 200G, and a power density of 1 to 40W/cm2。
8. The preparation method according to claim 6, wherein in the step (b), the doping mass ratio of the metal oxide having hole injection capability, the copper compound and the hole-doped guest material is 10:5:1 to 40:10: 1.
9. The method according to claim 6, wherein in the step (b), the electron beam evaporation energy density of the electron beam evaporation apparatus is 10 to l00W/cm2The thickness of the ternary doping layer is 50-300 nm.
10. The method according to claim 6, wherein in the step (c), the evaporation rate of the hole transport layer, the emission layer and the electron transport layer is 0.1 to 1nm/s, and the evaporation rate of the cathode layer is 1 to 10 nm/s.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106960910A (en) * | 2017-04-09 | 2017-07-18 | 晋芳芳 | A kind of long-life organic ultraviolet photodetector and preparation method thereof |
| CN109585685A (en) * | 2018-12-07 | 2019-04-05 | 纳晶科技股份有限公司 | Light takes out structure, its production method and luminescent device |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106960910A (en) * | 2017-04-09 | 2017-07-18 | 晋芳芳 | A kind of long-life organic ultraviolet photodetector and preparation method thereof |
| CN106960910B (en) * | 2017-04-09 | 2019-10-29 | 栾静远 | A kind of long-life organic ultraviolet photodetector and preparation method thereof |
| CN109585685A (en) * | 2018-12-07 | 2019-04-05 | 纳晶科技股份有限公司 | Light takes out structure, its production method and luminescent device |
| CN109585685B (en) * | 2018-12-07 | 2021-06-01 | 纳晶科技股份有限公司 | Light extraction structure, manufacturing method thereof and light emitting device |
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