CN104638183A - Transparent organic light-emitting device and method for manufacturing same - Google Patents
Transparent organic light-emitting device and method for manufacturing same Download PDFInfo
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- CN104638183A CN104638183A CN201310561897.0A CN201310561897A CN104638183A CN 104638183 A CN104638183 A CN 104638183A CN 201310561897 A CN201310561897 A CN 201310561897A CN 104638183 A CN104638183 A CN 104638183A
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 230000004888 barrier function Effects 0.000 claims abstract description 109
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 104
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000010703 silicon Substances 0.000 claims abstract description 103
- 239000000463 material Substances 0.000 claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 30
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 15
- 239000011368 organic material Substances 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 88
- 238000002360 preparation method Methods 0.000 claims description 77
- 239000007789 gas Substances 0.000 claims description 67
- 238000002156 mixing Methods 0.000 claims description 47
- 229910052786 argon Inorganic materials 0.000 claims description 44
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 36
- 238000007254 oxidation reaction Methods 0.000 claims description 34
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- 238000001755 magnetron sputter deposition Methods 0.000 claims description 20
- 238000005229 chemical vapour deposition Methods 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 238000001704 evaporation Methods 0.000 claims description 18
- 230000008020 evaporation Effects 0.000 claims description 18
- 238000005401 electroluminescence Methods 0.000 claims description 17
- -1 FePC Chemical compound 0.000 claims description 16
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical group [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 238000007738 vacuum evaporation Methods 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 12
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims description 12
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 12
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical group [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052581 Si3N4 Inorganic materials 0.000 claims description 10
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- 238000004020 luminiscence type Methods 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
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- 239000011777 magnesium Substances 0.000 claims description 8
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
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- 239000004411 aluminium Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 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
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 claims description 5
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
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- 239000011572 manganese Substances 0.000 claims description 5
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical class C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 5
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 4
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 4
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 claims description 4
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000377 silicon dioxide Substances 0.000 claims description 2
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- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims 2
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- DIVZFUBWFAOMCW-UHFFFAOYSA-N 4-n-(3-methylphenyl)-1-n,1-n-bis[4-(n-(3-methylphenyl)anilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 DIVZFUBWFAOMCW-UHFFFAOYSA-N 0.000 description 6
- 229910004261 CaF 2 Inorganic materials 0.000 description 6
- 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 description 6
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
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- 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
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- 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 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a transparent organic light-emitting device which comprises a transparent anode conductive substrate, an organic light-emitting functional layer, a transparent cathode layer and a packaging layer. The transparent anode conductive substrate, the organic light-emitting functional layer, the transparent cathode layer and the packaging layer are sequentially stacked; the packaging layer comprises a mixed barrier layer, a first silicon oxynitride layer, an inorganic barrier layer and a second silicon oxynitride layer which are sequentially stacked; the mixed barrier layer is made of a mixed material of metal phthalocyanine complexes, organic materials and metal fluorides; the inorganic barrier layer is made of hydrogenated oxides. The transparent organic light-emitting device has the advantages that the packaging layer of the transparent organic light-emitting device is excellent in water and oxygen barrier property and light transmission, the minimum water vapor permeability of the packaged device is only 5.51*10<-6>g/m<2>.day, the service life of the transparent organic light-emitting device reaches 20,000 hours (under the condition of T70@1000cd/m<2>) at least, and the light transmission of a packaged surface reaches 38% at least. The invention further provides a method for manufacturing the transparent organic light-emitting device.
Description
Technical field
The invention belongs to organic electroluminescence device field, be specifically related to a kind of transparent organic electroluminescent device and preparation method thereof.
Background technology
Electroluminescent organic material in organic electroluminescence device (OLED) invades responsive especially to oxygen and steam, on the one hand because oxygen is quencher, luminous quantum efficiency can be made significantly to decline, and oxygen also can make its transmittability decline to the oxidation of hole transmission layer; On the other hand, the main failure mode of steam is the hydrolysis of organic compound, its stability is declined greatly, thus causes component failure.Thus; the degeneration of effective suppression OLED in long-term work process and inefficacy; make the life-span that its steady operation reaches enough; this proposes high requirement to the barrier of encapsulating material; and the encapsulation technology playing seal protection effect has just become the break-through point solving OLED life problems; encapsulation technology is the interlayer by forming compact structure, realizes physical protection to the core component in encapsulation region.
Transparent organic electroluminescent device (TOLED) is the one of organic electroluminescence device, it not only can simultaneously from anode and negative electrode lighting at two sides, and the penetrability had to a certain degree, can the background at display frame rear, be applicable to building and vehicle window, shopper window and glasses etc., be with a wide range of applications.Therefore, the encapsulated layer of transparent organic electroluminescent device, except will possessing the good sealing of common OLED encapsulated layer, also needs to have good encapsulating face light transmittance.
Flexible product is the development trend of transparent organic electroluminescent device, and the barrier property of flexible device plastic-substrates usually used all cannot reach the requirement of TOLED encapsulation, the problem that therefore the flexible and transparent organic electroluminescence device ubiquity life-span is short.Given this, solving problems faced in flexible and transparent organic electroluminescence device encapsulation process, is the key promoting flexible TOLED production development.
Summary of the invention
The invention provides a kind of transparent organic electroluminescent device, the encapsulated layer of this transparent organic electroluminescent device replaces composite construction for mixing barrier layer/the first silicon oxynitride layer/inorganic barrier layer/the second silicon oxynitride layer, there is excellent water and oxygen barrier property and light transmission, the life-span of transparent organic electroluminescent device is made to reach 20, more than 000 hour (T70@1000cd/m
2), encapsulating face light transmittance reaches more than 38%.Present invention also offers a kind of preparation method of transparent organic electroluminescent device, the method technique is simple, easy large area preparation and mass production; The inventive method is applicable to encapsulate the transparent organic electroluminescent device prepared with conducting glass substrate, also be applicable to encapsulate the flexible and transparent organic electroluminescence device prepared for substrate with plastics or metal, be particularly useful for encapsulation flexible and transparent organic electroluminescence device.
First aspect, the invention provides a kind of transparent organic electroluminescent device, comprise transparent anode electrically-conductive backing plate and at transparent anode electrically-conductive backing plate surface the organic luminescence function layer, transparent cathode and the encapsulated layer that are cascading, described encapsulated layer comprise be cascading mixing barrier layer, the first silicon oxynitride layer, inorganic barrier layer and the second silicon oxynitride layer;
The material on described mixing barrier layer is the composite material that metal phthalocyanine complex, metal fluoride and organic material are formed; Described metal phthalocyanine complex is at least one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc), FePC (FePc), Cobalt Phthalocyanine (CoPc), manganese phthalocyanine (MnPc) and Nickel Phthalocyanine (NiPc), and described metal fluoride is lithium fluoride (LiF), cerium fluoride (CeF
3), magnesium fluoride (MgF
2), aluminum fluoride (AlF
3), calcirm-fluoride (CaF
2) and barium fluoride (BaF
2) at least one, described organic material is 1,1-bis-((4-N, N '-two (p-methylphenyl) amine) phenyl) cyclohexane (TAPC), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), oxine aluminium (Alq3), 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi);
The material of described first silicon oxynitride layer and the second silicon oxynitride layer is silicon nitride compound;
The material of described inorganic barrier layer is at least one in hydro-oxidation titanium, hydro-oxidation magnesium, hydrogenated silicon dioxide, hydro-oxidation zirconium, hydro-oxidation zinc and hydrogenated aluminum oxides.
The material of described first silicon oxynitride layer and the second silicon oxynitride layer is silicon nitride compound (SiO
xn
ywherein 0.01 < x≤1.5,0.01 < y≤1.3,0.5 < x+y < 2.5), described first silicon oxynitride layer and the second silicon oxynitride layer are the noncrystalline membrane with diamond-like, described silicon nitride compound has inorganic matter and organic double grading, has the high water resistance of inorganic matter and organic pliability concurrently; O, atom N and to adjoin Si atom be tetrahedron bonding in silicon nitride laminate structures, compact structure and stability is strong, corrosion resistance is strong, so have excellent barrier property; The pliability of silicon oxynitride layer can consumable film ply stress, avoids the appearance of the defect such as space, crack, is conducive to the realization of flexible package; On the other hand, silicon nitride compound has good light transmission, is conducive to the raising of transparent organic electroluminescent device encapsulating face light transmittance; And silicon oxynitride layer repeat preparation, not only can strengthen packaging effect, the pliability of encapsulating structure can also be increased, alleviate the quality of device, make device portability more.
The material of described inorganic barrier layer is inclusion of hydroperoxide rete, and oxide membranous layer is generally dense, has excellent water oxygen barrier properties, but oxidation film is general more crisp, and usually forms the rete of graininess distribution, and pin hole is many; Through over hydrogenation, oxide image height molecule can be made equally crosslinked, easily form continuous, even, smooth film layer structure, reduce pin hole and gap, not only can strengthen barrier properties, also be conducive to the raising of encapsulating face light transmittance; On the other hand, the surface of inclusion of hydroperoxide rete can produce more Lacking oxygen, and these Lacking oxygen can adsorb extraneous steam and oxygen, make up Lacking oxygen, make the more perfect densification of film layer structure, steam and oxygen device inside more difficult to get access are caused damage.
Preferably, the molar fraction of metal phthalocyanine compound described in described mixing barrier layer shared by described composite material is 40% ~ 60%, and the molar fraction of described metal fluoride shared by described composite material is 10% ~ 30%.
Described mixing barrier layer adopts organic-inorganic composite material, and metal phthalocyanine compound evenness is very high, even film layer can be made continuous, and have good adhesive force between transparent cathode; Metal fluoride chemically stable is good and anti-corrosion capability strong, adding of metal fluoride, makes rete finer and close, both the deficiency of simple organic material barrier property difference can have been made up, can have complementary advantages again, synergy, realizes all having excellent barrier property to oxygen and steam.On the other hand, metal phthalocyanine complex is polycrystalline structure, has very strong scattering process to light, can improve the light transmission rate of transparent light-emitting device encapsulating face.
Preferably, the thickness on described mixing barrier layer is 100nm ~ 200nm, and the thickness of described first silicon oxynitride layer is 150nm ~ 200nm, and the thickness of described inorganic barrier layer is 50nm ~ 100nm, and the thickness of described second silicon oxynitride layer is 150nm ~ 200nm.
Preferably, described transparent anode electrically-conductive backing plate is transparent conducting glass substrate or electrically conducting transparent organic film substrate, more preferably, the material of described transparent conducting glass substrate is the one in indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO); The material of described electrically conducting transparent organic film substrate is the one in PETG (PET), polysulfones ether (PES), polyethylene naphthalate (PEN), polyimides (PI).
Preferably, described organic luminescence function layer comprises luminescent layer, and comprises at least one in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer.
On the other hand, the invention provides a kind of preparation method of transparent organic electroluminescent device, comprise the following steps:
(1) prepare the anode pattern of organic electroluminescence device on the transparent conductive substrate surface of cleaning, form transparent anode electrically-conductive backing plate;
(2) prepare organic luminescence function layer and transparent cathode by the mode of vacuum evaporation successively on transparent anode electrically-conductive backing plate surface, evaporation rate is
vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa;
(3) prepare encapsulated layer on transparent cathode surface, described encapsulated layer comprise be cascading mixing barrier layer, the first silicon oxynitride layer, inorganic barrier layer and the second silicon oxynitride layer, the preparation method of described encapsulated layer is as follows:
A () adopts the mode of vacuum evaporation on preparation mixing barrier layer, transparent cathode surface, the material on described mixing barrier layer is the composite material that metal phthalocyanine complex, metal fluoride and organic material are formed; Described metal phthalocyanine complex is at least one in CuPc (CuPc), Phthalocyanine Zinc (ZnPc), FePC (FePc), Cobalt Phthalocyanine (CoPc), manganese phthalocyanine (MnPc) and Nickel Phthalocyanine (NiPc), and described metal fluoride is lithium fluoride (LiF), cerium fluoride (CeF
3), magnesium fluoride (MgF
2), aluminum fluoride (AlF
3), calcirm-fluoride (CaF
2) and barium fluoride (BaF
2) at least one, described organic material is 1,1-bis-((4-N, N '-two (p-methylphenyl) amine) phenyl) cyclohexane (TAPC), N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), oxine aluminium (Alq3), 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi);
B () adopts the method for plasma reinforced chemical vapour deposition to prepare the first silicon oxynitride layer at mixing barrier layer surface, the material of described first silicon oxynitride layer is silicon nitride compound;
C () adopts the mode of magnetron sputtering to prepare inorganic barrier layer on the first silicon oxynitride layer surface, the material of described inorganic barrier layer is at least one in hydro-oxidation titanium, hydro-oxidation magnesium, hydrogenated silicon dioxide, hydro-oxidation zirconium, hydro-oxidation zinc and hydrogenated aluminum oxides;
D () adopts the method for plasma reinforced chemical vapour deposition at inorganic barrier layer surface preparation the second silicon oxynitride layer, the material of described second silicon oxynitride layer is silicon nitride compound.
Preferably, the molar fraction of metal phthalocyanine compound described in step (a) shared by described composite material is 40% ~ 60%, and the molar fraction of described metal fluoride shared by described composite material is 10% ~ 30%.
Preferably, the thickness mixing barrier layer described in step (a) is 100nm ~ 200nm, the thickness of the first silicon oxynitride layer described in step (b) is 150nm ~ 200nm, the thickness of inorganic barrier layer described in step (c) is 50nm ~ 100nm, and the thickness of the second silicon oxynitride layer described in step (d) is 150nm ~ 200nm.
Preferably, the process conditions of vacuum evaporation described in step (a) are: vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is
Preferably, step (b) with the process conditions of plasma reinforced chemical vapour deposition process described in step (d) is: adopt hmds (HMDS), ammonia (NH
3) and oxygen (O
2) as reacting gas, argon gas (Ar) is carrier gas, the flow controlling hmds (HMDS) is 6sccm ~ 14sccm, ammonia (NH
3) flow be 2sccm ~ 18sccm, oxygen (O
2) flow be 2sccm ~ 18sccm, the flow of argon gas (Ar) is 70sccm ~ 80sccm, and control operating pressure is 10Pa ~ 50Pa, and radio-frequency power is 0.1W/cm
2~ 1W/cm
2.
In described step (b) and (d), using plasma strengthens chemical vapour deposition technique and prepares silicon oxynitride layer, and major advantage is that depositing temperature is low, to the structure of matrix and impact on physical properties little; The thickness of film and homogeneity of ingredients good, membrane tissue is fine and close, pin hole is few, strong to the obstructing capacity of steam and oxygen; The strong adhesion of rete, effectively can avoid the device failure that steam and oxygen infiltrate from interface and brings.
Preferably, titanium oxide (TiO is adopted in magnetron sputtering process described in step (c)
2), magnesium oxide (MgO), silicon dioxide (SiO
2), zirconia (ZrO
2), zinc oxide (ZnO) and aluminium oxide (Al
2o
3) at least one as target, methane is reacting gas, and argon gas is carrier gas.
Adopt metal oxide as target, the rete density obtained is high, and defect is few; Methane, as reacting gas, not only can make oxide surface hydrogenation, and methane is safe, nontoxic, is more conducive to industrial production; The hydrogenation of oxidation film makes oxide more easily form the rete of uniformly continous, reduces the generation in pin hole or gap, improves barrier property.
Preferably, the flow controlling argon gas in above-mentioned magnetron sputtering process is 5sccm ~ 15sccm, and the flow of methane is 10sccm ~ 20sccm, and the accelerating voltage of magnetron sputtering controls at 300V ~ 800V, and magnetic flux density is 50G ~ 200G, and power density is 10W/cm
2~ 40W/cm
2, target-substrate distance is 50mm ~ 80mm, and background vacuum is 1 × 10
-5pa ~ 1 × 10
-3pa.
Preferably, described transparent conductive substrate is transparent conducting glass substrate or electrically conducting transparent organic film substrate, more preferably, the material of described transparent conducting glass substrate is the one in indium tin oxide (ITO), aluminium zinc oxide (AZO) or indium-zinc oxide (IZO); The material of described electrically conducting transparent organic film substrate is the one in PETG (PET), polysulfones ether (PES), polyethylene naphthalate (PEN), polyimides (PI).
Preferably, described organic luminescence function layer comprises luminescent layer, and comprises at least one in hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer.
Compared with prior art, its beneficial effect is embodied in the following aspects in the present invention:
(1) encapsulated layer of the present invention adopts mixing barrier layer/the first silicon oxynitride layer/inorganic barrier layer/the second silicon oxynitride layer multi-layer compound structure, both the length of steam and oxygen infiltration " passage " can have been increased, strengthen the effect on barrier layer, layers of material iris action is excellent simultaneously, while exerting advantages of oneself, also have complementary advantages, the only encapsulated layer of hundreds of nanometer thickness, just effectively can stop the erosion of oxygen and steam, the transparent organic electroluminescent device after encapsulation vapor permeability (WVTR) be minimumly only 5.51 × 10
-6g/m
2day, the life-span reaches 20, more than 000 hour (T70@1000cd/m
2).
(2) in the present invention, the first silicon oxynitride layer and the second silicon oxynitride layer have the double grading of organic-inorganic material, have excellent barrier property and stress slow releasing function concurrently, the weight of device can also be alleviated, make device portability more, be conducive to the flexible package of device.
(3) the encapsulated layer material that the present invention adopts all has good light transmission, and interphase match between layers, encapsulated layer general thickness only has hundreds of nanometer, greatly reduces light in transparent devices and, from the loss of encapsulating face outgoing, makes the light transmittance of transparent devices encapsulating face more than 38%.
(4) the inventive method is applicable to encapsulate the transparent organic electroluminescent device prepared with conducting glass substrate, also be applicable to encapsulate the flexible and transparent organic electroluminescence device prepared for substrate with plastics or metal, the inventive method is particularly useful for encapsulation flexible and transparent organic electroluminescence device.
(5) preparation method's technique provided by the invention is simple, and automaticity is high, easy large area preparation and mass production.
Accompanying drawing explanation
Fig. 1 is the structural representation of transparent organic electroluminescent device in embodiment 1.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
Fig. 1 is the structural representation of a kind of transparent organic electroluminescent device that the present embodiment provides.As shown in Figure 1, this transparent organic electroluminescent device, comprises the transparent conducting glass substrate 10, organic luminescence function layer 20, transparent cathode 30 and the encapsulated layer 40 that are cascading from lower to upper.Wherein, described organic luminescence function layer 20 comprises the hole injection layer 21, hole transmission layer 22, luminescent layer 23, electron transfer layer 24 and the electron injecting layer 25 that are cascading from bottom to top; Described encapsulated layer 40 comprises mixing barrier layer 41, first silicon oxynitride layer 42, inorganic barrier layer 43 and the second silicon oxynitride layer 44 that are cascading.
The preparation method of this transparent organic electroluminescent device, comprises the following steps:
(1) ito glass substrate 10 pre-treatment: ito glass substrate, successively through acetone, ethanol, deionized water, ethanol purge, all cleans with supersonic wave cleaning machine, individual event washing cleaning 5 minutes, then dry up with nitrogen, stove-drying is stand-by; Also need to carry out surface activation process to the ito glass after cleaning, to increase the oxygen content of conductive surface layer, improve the work function of conductive layer surface; ITO thickness is 100nm;
(2) organic luminescence function layer 20 and transparent cathode 30 is prepared by the mode of vacuum evaporation successively on described conducting glass substrate 10 surface:
The preparation of hole injection layer 21: material is MoO
3be entrained in N, the composite material formed in N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB), MoO
3mass fraction shared in described composite material is 30%, and thickness is 10nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of hole transmission layer 22: material is 4,4', 4''-tri-(carbazole-9-base) triphenylamine (TCTA), evaporation thickness 30nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of luminescent layer 23: material of main part adopts 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI), guest materials adopts three (2-phenylpyridines) to close iridium (Ir (ppy)
3), the doping mass fraction of guest materials is 5%, evaporation thickness 20nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of electron transfer layer 24: material is 4,7-diphenyl-1,10-phenanthroline (Bphen), and thickness is 10nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of electron injecting layer 25: material is CsN
3be entrained in the composite material formed in Bphen, CsN
3mass fraction shared in described composite material is 30%, and thickness is 20nm, vacuum degree 1 × 10
-5pa, evaporation rate
The preparation of transparent cathode 30: it is 10nm that transparent cathode adopts ZnS/Ag/ZnS, ZnS layer thickness to be 30nm, Ag layer thickness, and vacuum degree is 1 × 10
-5pa, evaporation rate
(3) preparation of encapsulated layer 40:
The preparation on (a) mixing barrier layer 41: adopt the mode of vacuum evaporation on preparation mixing barrier layer 41, transparent cathode 30 surface, the material on described mixing barrier layer is CuPc (CuPc), lithium fluoride (LiF) and 1,1-bis-((4-N, N '-two (p-methylphenyl) amine) phenyl) composite material (being expressed as CuPc:LiF:TAPC) that formed of cyclohexane (TAPC), the molar fraction that wherein CuPc, LiF are shared in described composite material is respectively 50%, 30%; The vacuum degree adopted is 1 × 10
-5pa, evaporation rate is
thickness is 200nm;
(b) first preparation of silicon oxynitride layer 42: adopt the method for plasma reinforced chemical vapour deposition at mixing barrier layer 41 surface preparation the first silicon oxynitride layer 42; Adopt hmds (HMDS), ammonia (NH
3) and oxygen (O
2) as reacting gas, argon gas (Ar) is carrier gas, controls hmds (HMDS), ammonia (NH
3), oxygen (O
2) and the flow of argon gas (Ar) respectively be 10sccm, 10sccm, 10sccm, 75sccm, operating pressure is 40Pa, and radio-frequency power is 0.5W/cm
2, deposit thickness is 200nm;
The preparation of (c) inorganic barrier layer 43: adopt the mode of magnetron sputtering to prepare inorganic barrier layer 43 on the first silicon oxynitride layer 42 surface; The material of described inorganic barrier layer is hydro-oxidation titanium, adopts TiO
2as target, methane is reacting gas, and argon gas is carrier gas; The flow controlling argon gas and methane is respectively 10sccm, 20sccm, and the accelerating voltage of magnetron sputtering controls at 500V, and magnetic flux density is 100G, and power density is 20W/cm
2, target-substrate distance is 60mm, and background vacuum is 1 × 10
-5pa, thickness is 100nm;
(d) second preparation of silicon oxynitride layer 44: adopt the method for plasma reinforced chemical vapour deposition at inorganic barrier layer 43 surface preparation the second silicon oxynitride layer 44; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, control HMDS, NH
3, O
2respectively be 10sccm, 10sccm, 10sccm, 75sccm with the flow of argon gas, operating pressure is 40Pa, and radio-frequency power is 0.5W/cm
2, deposit thickness is 200nm.
The encapsulated layer 40 of transparent organic electroluminescent device prepared by the present embodiment comprises the CuPc:LiF:TAPC layer 41 that the thickness be cascading is 200nm, thickness is first silicon oxynitride layer 42 of 200nm, second silicon oxynitride layer 44 of thickness to be the hydro-oxidation titanium layer 43 of 100nm and thickness be 200nm, described encapsulated layer 40 is CuPc:LiF:TAPC layer/the first silicon oxynitride layer/hydro-oxidation titanium layer/the second silicon oxynitride layer multi-layer compound structure, and general thickness is 700nm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the transparent organic electroluminescent device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 5.51 × 10
-6g/m
2day, the life-span is 20,144 hours.
Embodiment 2
There is a preparation method for transparent plane electroluminescent device, comprise the following steps:
(1), (2) are with embodiment 1;
(3) preparation of encapsulated layer:
The preparation on (a) mixing barrier layer: adopt the mode of vacuum evaporation on preparation mixing barrier layer, transparent cathode surface, the material on described mixing barrier layer is Phthalocyanine Zinc (ZnPc), CeF
3with the composite material that N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines (NPB) is formed (is expressed as ZnPc:CeF
3: NPB), wherein ZnPc, CeF
3molar fraction shared in described composite material is respectively 40%, 15%; The vacuum degree adopted is 5 × 10
-5pa, evaporation rate is
thickness is 150nm;
(b) first preparation of silicon oxynitride layer: adopt the method for plasma reinforced chemical vapour deposition to prepare the first silicon oxynitride layer at mixing barrier layer surface; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, controls hmds (HMDS), NH
3, O
2respectively be 12sccm, 15sccm, 10sccm, 77sccm with the flow of argon gas, operating pressure is 10Pa, and radio-frequency power is 0.1W/cm
2, deposit thickness is 180nm;
The preparation of (c) inorganic barrier layer: adopt the mode of magnetron sputtering to prepare inorganic barrier layer on the first silicon oxynitride layer surface; The material of described inorganic barrier layer is hydro-oxidation magnesium, and adopt MgO as target, methane is reacting gas, and argon gas is carrier gas; The flow controlling argon gas and methane is respectively 5sccm, 15sccm, and the accelerating voltage of magnetron sputtering controls at 300V, and magnetic flux density is 50G, and power density is 10W/cm
2, target-substrate distance is 50mm, and background vacuum is 1 × 10
-5pa, thickness is 50nm;
(d) second preparation of silicon oxynitride layer: adopt the method for plasma reinforced chemical vapour deposition at inorganic barrier layer surface preparation the second silicon oxynitride layer; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, control HMDS, NH
3, O
2respectively be 12sccm, 15sccm, 10sccm, 77sccm with the flow of argon gas, operating pressure is 10Pa, and radio-frequency power is 0.1W/cm
2, deposit thickness is 180nm.
It is the ZnPc:CeF of 150nm that the encapsulated layer of transparent organic electroluminescent device prepared by the present embodiment comprises the thickness be cascading
3: NPB layer, thickness is first silicon oxynitride layer of 180nm, and second silicon oxynitride layer of thickness to be the hydro-oxidation magnesium layer of 50nm and thickness be 180nm, described encapsulated layer is ZnPc:CeF
3: NPB layer/the first silicon oxynitride layer/hydro-oxidation magnesium layer/the second silicon oxynitride layer multi-layer compound structure, general thickness is 560nm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the transparent organic electroluminescent device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 5.53 × 10
-6g/m
2day, the life-span is 20,100 hours.
Embodiment 3
There is a preparation method for transparent plane electroluminescent device, comprise the following steps:
(1), (2) are with embodiment 1;
(3) preparation of encapsulated layer:
The preparation on (a) mixing barrier layer: adopt the mode of vacuum evaporation on preparation mixing barrier layer, transparent cathode surface, the material on described mixing barrier layer is FePC (FePc), MgF
2(FePc:MgF is expressed as with the composite material that oxine aluminium (Alq3) is formed
2: Alq3), wherein FePc, MgF
2molar fraction shared in described composite material is respectively 60%, 10%; The vacuum degree adopted is 5 × 10
-5pa, evaporation rate is
thickness is 100nm;
(b) first preparation of silicon oxynitride layer: adopt the method for plasma reinforced chemical vapour deposition to prepare the first silicon oxynitride layer at mixing barrier layer surface; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, controls hmds (HMDS), NH
3, O
2respectively be 8sccm, 5sccm, 8sccm, 75sccm with the flow of argon gas, operating pressure is 50Pa, and radio-frequency power is 1W/cm
2, deposit thickness is 170nm;
The preparation of (c) inorganic barrier layer: adopt the mode of magnetron sputtering to prepare inorganic barrier layer on the first silicon oxynitride layer surface; The material of described inorganic barrier layer is hydrogenated silicon dioxide, adopts SiO
2as target, methane is reacting gas, and argon gas is carrier gas; The flow controlling argon gas and methane is respectively 7sccm, 10sccm, and the accelerating voltage of magnetron sputtering controls at 800V, and magnetic flux density is 200G, and power density is 40W/cm
2, target-substrate distance is 80mm, and background vacuum is 1 × 10
-5pa, thickness is 70nm;
(d) second preparation of silicon oxynitride layer: adopt the method for plasma reinforced chemical vapour deposition at inorganic barrier layer surface preparation the second silicon oxynitride layer; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, control HMDS, NH
3, O
2respectively be 8sccm, 5sccm, 8sccm, 75sccm with the flow of argon gas, operating pressure is 50Pa, and radio-frequency power is 1W/cm
2, deposit thickness is 170nm.
It is the FePc:MgF of 100nm that the encapsulated layer of transparent organic electroluminescent device prepared by the present embodiment comprises the thickness be cascading
2: Alq3 layer, thickness is first silicon oxynitride layer of 170nm, and second silicon oxynitride layer of thickness to be the hydro-oxidation magnesium layer of 70nm and thickness be 170nm, described encapsulated layer is FePc:MgF
2: Alq3 layer/the first silicon oxynitride layer/hydrogenated silicon dioxide layer/the second silicon oxynitride layer multi-layer compound structure, general thickness is 510nm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the transparent organic electroluminescent device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 5.54 × 10
-6g/m
2day, the life-span is 20,064 hour.
Embodiment 4
There is a preparation method for transparent plane electroluminescent device, comprise the following steps:
(1), (2) are with embodiment 1;
(3) preparation of encapsulated layer:
The preparation on (a) mixing barrier layer: adopt the mode of vacuum evaporation on preparation mixing barrier layer, transparent cathode surface, the material on described mixing barrier layer is Cobalt Phthalocyanine (CoPc), AlF
3(CoPc:AlF is expressed as with the composite material that 4,4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine (m-MTDATA) is formed
3: m-MTDATA), wherein CoPc, AlF
3molar fraction shared in described composite material is respectively 50%, 20%; The vacuum degree adopted is 5 × 10
-5pa, evaporation rate is
thickness is 150nm;
(b) first preparation of silicon oxynitride layer: adopt the method for plasma reinforced chemical vapour deposition to prepare the first silicon oxynitride layer at mixing barrier layer surface; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, controls hmds (HMDS), NH
3, O
2respectively be 14sccm, 18sccm, 18sccm, 70sccm with the flow of argon gas, operating pressure is 20Pa, and radio-frequency power is 0.5W/cm
2, deposit thickness is 160nm;
The preparation of (c) inorganic barrier layer: adopt the mode of magnetron sputtering to prepare inorganic barrier layer on the first silicon oxynitride layer surface; The material of described inorganic barrier layer is hydro-oxidation zirconium, adopts ZrO
2as target, methane is reacting gas, and argon gas is carrier gas; The flow controlling argon gas and methane is respectively 15sccm, 15sccm, and the accelerating voltage of magnetron sputtering controls at 400V, and magnetic flux density is 100G, and power density is 30W/cm
2, target-substrate distance is 60mm, and background vacuum is 5 × 10
-5pa, thickness is 100nm;
(d) second preparation of silicon oxynitride layer: adopt the method for plasma reinforced chemical vapour deposition at inorganic barrier layer surface preparation the second silicon oxynitride layer; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, and the flow of control HMDS, NH3, O2 and argon gas respectively is 14sccm, 18sccm, 18sccm, 70sccm, and operating pressure is 20Pa, and radio-frequency power is 0.5W/cm
2, deposit thickness is 160nm.
It is the CoPc:AlF of 150nm that the encapsulated layer of transparent organic electroluminescent device prepared by the present embodiment comprises the thickness be cascading
3: m-MTDATA layer, thickness is first silicon oxynitride layer of 160nm, and second silicon oxynitride layer of thickness to be the hydro-oxidation zirconium layer of 100nm and thickness be 160nm, described encapsulated layer is CoPc:AlF
3: m-MTDATA layer/the first silicon oxynitride layer/hydro-oxidation zirconium layer/the second silicon oxynitride layer multi-layer compound structure, general thickness is 570nm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the transparent organic electroluminescent device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 5.55 × 10
-6g/m
2day, the life-span is 20,041 hour.
Embodiment 5
There is a preparation method for transparent plane electroluminescent device, comprise the following steps:
(1), (2) are with embodiment 1;
(3) preparation of encapsulated layer:
The preparation on (a) mixing barrier layer: adopt the mode of vacuum evaporation on preparation mixing barrier layer, transparent cathode surface, the material on described mixing barrier layer is manganese phthalocyanine (MnPc), CaF
2, the composite material that formed of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) (is expressed as MnPc:CaF
2: BCP), wherein MnPc, CaF
2molar fraction shared in described composite material is respectively 55%, 15%; The vacuum degree adopted is 5 × 10
-5pa, evaporation rate is
thickness is 150nm;
(b) first preparation of silicon oxynitride layer: adopt the method for plasma reinforced chemical vapour deposition to prepare the first silicon oxynitride layer at mixing barrier layer surface; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, controls hmds (HMDS), NH
3, O
2respectively be 6sccm, 2sccm, 2sccm, 80sccm with the flow of argon gas, operating pressure is 30Pa, and radio-frequency power is 0.8W/cm
2, deposit thickness is 150nm;
The preparation of (c) inorganic barrier layer: adopt the mode of magnetron sputtering to prepare inorganic barrier layer on the first silicon oxynitride layer surface; The material of described inorganic barrier layer is hydro-oxidation zinc, and adopt ZnO as target, methane is reacting gas, and argon gas is carrier gas; The flow controlling argon gas and methane is respectively 5sccm, 20sccm, and the accelerating voltage of magnetron sputtering controls at 600V, and magnetic flux density is 150G, and power density is 30W/cm
2, target-substrate distance is 70mm, and background vacuum is 5 × 10
-5pa, thickness is 80nm;
(d) second preparation of silicon oxynitride layer: adopt the method for plasma reinforced chemical vapour deposition at inorganic barrier layer surface preparation the second silicon oxynitride layer; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, control HMDS, NH
3, O
2respectively be 6sccm, 2sccm, 2sccm, 80sccm with the flow of argon gas, operating pressure is 30Pa, and radio-frequency power is 0.8W/cm
2, deposit thickness is 150nm.
It is the MnPc:CaF of 150nm that the encapsulated layer of transparent organic electroluminescent device prepared by the present embodiment comprises the thickness be cascading
2: BCP layer, thickness is first silicon oxynitride layer of 150nm, and second silicon oxynitride layer of thickness to be the hydro-oxidation zinc layers of 80nm and thickness be 150nm, described encapsulated layer is MnPc:CaF
2: BCP layer/the first silicon oxynitride layer/hydro-oxidation zinc layers/the second silicon oxynitride layer multi-layer compound structure, general thickness is 530nm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the transparent organic electroluminescent device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 5.56 × 10
-6g/m
2day, the life-span is 20,023 hour.
Embodiment 6
There is a preparation method for transparent plane electroluminescent device, comprise the following steps:
(1), (2) are with embodiment 1;
(3) preparation of encapsulated layer:
The preparation on (a) mixing barrier layer: adopt the mode of vacuum evaporation on preparation mixing barrier layer, transparent cathode surface, the material on described mixing barrier layer is Nickel Phthalocyanine (NiPc), BaF
2(NiPc:BaF is expressed as with the composite material that 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBi) is formed
2: TPBi), wherein NiPc, BaF
2molar fraction shared in described composite material is respectively 60%, 16%; The vacuum degree adopted is 1 × 10
-3pa, evaporation rate is
thickness is 150nm;
(b) first preparation of silicon oxynitride layer: adopt the method for plasma reinforced chemical vapour deposition to prepare the first silicon oxynitride layer at mixing barrier layer surface; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, controls hmds (HMDS), NH
3, O
2respectively be 6sccm, 15sccm, 5sccm, 75sccm with the flow of argon gas, operating pressure is 35Pa, and radio-frequency power is 0.7W/cm
2, deposit thickness is 160nm;
The preparation of (c) inorganic barrier layer: adopt the mode of magnetron sputtering to prepare inorganic barrier layer on the first silicon oxynitride layer surface; The material of described inorganic barrier layer is hydrogenated aluminum oxides, adopts Al
2o
3as target, methane is reacting gas, and argon gas is carrier gas; The flow controlling argon gas and methane is respectively 7sccm, 13sccm, and the accelerating voltage of magnetron sputtering controls at 500V, and magnetic flux density is 200G, and power density is 40W/cm
2, target-substrate distance is 75mm, and background vacuum is 1 × 10
-3pa, thickness is 70nm;
(d) second preparation of silicon oxynitride layer: adopt the method for plasma reinforced chemical vapour deposition at inorganic barrier layer surface preparation the second silicon oxynitride layer; Adopt hmds (HMDS), NH
3and O
2as reacting gas, argon gas is carrier gas, control HMDS, NH
3, O
2respectively be 6sccm, 15sccm, 5sccm, 75sccm with the flow of argon gas, operating pressure is 35Pa, and radio-frequency power is 0.7W/cm
2, deposit thickness is 160nm.
It is the NiPc:BaF of 150nm that the encapsulated layer of transparent organic electroluminescent device prepared by the present embodiment comprises the thickness be cascading
2: TPBi layer, thickness is first silicon oxynitride layer of 160nm, and second silicon oxynitride layer of thickness to be the hydro-oxidation aluminium lamination of 70nm and thickness be 160nm, described encapsulated layer is NiPc:BaF
2: TPBi layer/the first silicon oxynitride layer/hydro-oxidation aluminium lamination/the second silicon oxynitride layer multi-layer compound structure, general thickness is 540nm.
Be full of N
2in glove box, 20 ~ 25 DEG C of temperature, and water content and oxygen content be less than the condition of 1ppm under test the vapor permeability (WVTR) of the transparent organic electroluminescent device after the present embodiment encapsulation, the vapor permeability of the organic electroluminescence device that result shows after the present embodiment encapsulation is 5.59 × 10
-6g/m
2day, the life-span is 20,002 hour.
Effect example
For the beneficial effect of transparent organic electroluminescent device and preparation method thereof in valid certificates the present invention, the vapor permeability (WVTR) of test transparent organic electroluminescent device, and test (the T70@1000cd/m in useful life of transparent organic electroluminescent device
2), from original intensity 1000cd/m
2decay to the time needed for 70% and encapsulating face light transmittance.The embodiment of the present invention 1 ~ 6 prepare the vapor permeability of transparent organic electroluminescent device, useful life and encapsulating face light transmittance as shown in table 1.
The vapor permeability of transparent organic electroluminescent device prepared by table 1 embodiment 1 ~ 6, use longevity
Life and encapsulating face light transmittance
As can be seen from Table 1, the useful life of the transparent organic electroluminescent device after encapsulation technology encapsulation of the present invention reaches 20, more than 000 hour (T70@1000cd/m
2).This adopts mixing barrier layer/the first silicon oxynitride layer/inorganic barrier layer/the second silicon oxynitride layer to replace composite construction owing to encapsulated layer, both the length of steam and oxygen infiltration " passage " can have been increased, strengthen the effect on barrier layer, layers of material iris action is excellent simultaneously, while exerting advantages of oneself, also have complementary advantages, the only encapsulated layer of hundreds of nanometer thickness, just effectively can stop the erosion of oxygen and steam, make transparent organic electroluminescent device vapor permeability (WVTR) be all 10
-6g/m
2the day order of magnitude, minimumly reaches 5.51 × 10
-6g/m
2day, significant prolongation useful life of transparent organic electroluminescent device.
On the other hand, the encapsulated layer material that the present invention adopts all has good light transmission, and interphase match between layers, and encapsulated layer general thickness only has hundreds of nanometer, greatly reducing light in transparent devices, from the loss of encapsulating face outgoing, makes the light transmittance of transparent devices encapsulating face more than 38%.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a transparent organic electroluminescent device, the organic luminescence function layer, transparent cathode and the encapsulated layer that comprise transparent anode electrically-conductive backing plate and be cascading on transparent anode electrically-conductive backing plate, it is characterized in that, described encapsulated layer comprise be cascading mixing barrier layer, the first silicon oxynitride layer, inorganic barrier layer and the second silicon oxynitride layer;
The material on described mixing barrier layer is the composite material that metal phthalocyanine complex, metal fluoride and organic material are formed, described metal phthalocyanine complex is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, at least one in manganese phthalocyanine and Nickel Phthalocyanine, described metal fluoride is lithium fluoride, cerium fluoride, magnesium fluoride, aluminum fluoride, at least one in calcirm-fluoride and barium fluoride, described organic material is 1, 1-bis-((4-N, N '-two (p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines, oxine aluminium, 4, 4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline and 1, 3, at least one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene,
The material of described first silicon oxynitride layer and the second silicon oxynitride layer is silicon nitride compound;
The material of described inorganic barrier layer is at least one in hydro-oxidation titanium, hydro-oxidation magnesium, hydrogenated silicon dioxide, hydro-oxidation zirconium, hydro-oxidation zinc and hydrogenated aluminum oxides.
2. transparent organic electroluminescent device according to claim 1, it is characterized in that, the molar fraction of metal phthalocyanine compound described in described mixing barrier layer shared by described composite material is 40% ~ 60%, and the molar fraction of described metal fluoride shared by described composite material is 10% ~ 30%.
3. transparent organic electroluminescent device according to claim 1, it is characterized in that, the thickness on described mixing barrier layer is 100nm ~ 200nm, the thickness of described first silicon oxynitride layer is 150nm ~ 200nm, the thickness of described inorganic barrier layer is 50nm ~ 100nm, and the thickness of described second silicon oxynitride layer is 150nm ~ 200nm.
4. a preparation method for transparent organic electroluminescent device, is characterized in that, comprises the following steps:
(1) prepare the anode pattern of organic electroluminescence device on the transparent conductive substrate surface of cleaning, form transparent anode electrically-conductive backing plate;
(2) prepare organic luminescence function layer and transparent cathode by the mode of vacuum evaporation successively on transparent anode electrically-conductive backing plate surface, evaporation rate is
vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa;
(3) prepare encapsulated layer on transparent cathode surface, described encapsulated layer comprise be cascading mixing barrier layer, the first silicon oxynitride layer, inorganic barrier layer and the second silicon oxynitride layer, the preparation method of described encapsulated layer is as follows:
A () adopts the mode of vacuum evaporation on preparation mixing barrier layer, transparent cathode surface, the material on described mixing barrier layer is the composite material that metal phthalocyanine complex, metal fluoride and organic material are formed, described metal phthalocyanine complex is CuPc, Phthalocyanine Zinc, FePC, Cobalt Phthalocyanine, at least one in manganese phthalocyanine and Nickel Phthalocyanine, described metal fluoride is lithium fluoride, cerium fluoride, magnesium fluoride, aluminum fluoride, at least one in calcirm-fluoride and barium fluoride, described organic material is 1, 1-bis-((4-N, N '-two (p-methylphenyl) amine) phenyl) cyclohexane, N, N'-diphenyl-N, N'-bis-(1-naphthyl)-1, 1'-biphenyl-4, 4'-diamines, oxine aluminium, 4, 4', 4''-tri-(N-3-methylphenyl-N-phenyl is amino) triphenylamine, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline and 1, 3, at least one in 5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene,
B () adopts the method for plasma reinforced chemical vapour deposition to prepare the first silicon oxynitride layer at mixing barrier layer surface, the material of described first silicon oxynitride layer is silicon nitride compound;
C () adopts the mode of magnetron sputtering to prepare inorganic barrier layer on the first silicon oxynitride layer surface, the material of described inorganic barrier layer is at least one in hydro-oxidation titanium, hydro-oxidation magnesium, hydrogenated silicon dioxide, hydro-oxidation zirconium, hydro-oxidation zinc and hydrogenated aluminum oxides;
D () adopts the method for plasma reinforced chemical vapour deposition at inorganic barrier layer surface preparation the second silicon oxynitride layer, the material of described second silicon oxynitride layer is silicon nitride compound.
5. the preparation method of transparent organic electroluminescent device according to claim 4, it is characterized in that, the molar fraction of metal phthalocyanine compound described in step (a) shared by described composite material is 40% ~ 60%, and the molar fraction of described metal fluoride shared by described composite material is 10% ~ 30%.
6. the preparation method of transparent organic electroluminescent device according to claim 4, it is characterized in that, the thickness mixing barrier layer described in step (a) is 100nm ~ 200nm, the thickness of the first silicon oxynitride layer described in step (b) is 150nm ~ 200nm, the thickness of inorganic barrier layer described in step (c) is 50nm ~ 100nm, and the thickness of the second silicon oxynitride layer described in step (d) is 150nm ~ 200nm.
7. the preparation method of transparent organic electroluminescent device according to claim 4, is characterized in that, the process conditions of vacuum evaporation described in step (a) are: vacuum degree is 1 × 10
-5pa ~ 1 × 10
-3pa, evaporation rate is
8. the preparation method of transparent organic electroluminescent device according to claim 4, it is characterized in that, step (b) with the process conditions of plasma reinforced chemical vapour deposition process described in step (d) is: adopt hmds, ammonia and oxygen as reacting gas, argon gas is carrier gas, the flow controlling hmds is 6sccm ~ 14sccm, the flow of ammonia is 2sccm ~ 18sccm, the flow of oxygen is 2sccm ~ 18sccm, the flow of argon gas is 70sccm ~ 80sccm, control operating pressure is 10Pa ~ 50Pa, and radio-frequency power is 0.1W/cm
2~ 1W/cm
2.
9. the preparation method of transparent organic electroluminescent device according to claim 4, it is characterized in that, adopt at least one in titanium oxide, magnesium oxide, silicon dioxide, zirconia, zinc oxide and aluminium oxide as target in magnetron sputtering process described in step (c), methane is reacting gas, and argon gas is carrier gas.
10. the preparation method of the transparent organic electroluminescent device according to claim 4 and 9, it is characterized in that, magnetron sputtering process described in step (c), the flow controlling argon gas is 5sccm ~ 15sccm, the flow of methane is 10sccm ~ 20sccm, the accelerating voltage of magnetron sputtering controls at 300V ~ 800V, and magnetic flux density is 50G ~ 200G, and power density is 10W/cm
2~ 40W/cm
2, target-substrate distance is 50mm ~ 80mm, and background vacuum is 1 × 10
-5pa ~ 1 × 10
-3pa.
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| CN106886068A (en) * | 2015-12-16 | 2017-06-23 | 张家港康得新光电材料有限公司 | Optical filter, its preparation method with have its imaging device |
| CN107293646A (en) * | 2016-04-13 | 2017-10-24 | 上海和辉光电有限公司 | A kind of organic electroluminescence device and preparation method thereof |
| CN107293646B (en) * | 2016-04-13 | 2019-09-03 | 上海和辉光电有限公司 | A kind of organic electroluminescence device and preparation method thereof |
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Application publication date: 20150520 |