CN104078573A - Organic light-emitting diode device and packaging method thereof - Google Patents
Organic light-emitting diode device and packaging method thereof Download PDFInfo
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- 238000004806 packaging method and process Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000010410 layer Substances 0.000 claims abstract description 353
- 230000004888 barrier function Effects 0.000 claims abstract description 264
- 239000000463 material Substances 0.000 claims abstract description 146
- 239000000758 substrate Substances 0.000 claims abstract description 95
- 239000002346 layers by function Substances 0.000 claims abstract description 54
- 150000004767 nitrides Chemical class 0.000 claims abstract description 34
- 229910002064 alloy oxide Inorganic materials 0.000 claims abstract description 30
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 52
- 238000007738 vacuum evaporation Methods 0.000 claims description 44
- -1 α -naphthyl Chemical group 0.000 claims description 43
- 230000005525 hole transport Effects 0.000 claims description 36
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 24
- 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 22
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 22
- 238000005538 encapsulation Methods 0.000 claims description 21
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 20
- 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 claims description 19
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 19
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 19
- 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 17
- MZYDBGLUVPLRKR-UHFFFAOYSA-N 9-(3-carbazol-9-ylphenyl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC(N2C3=CC=CC=C3C3=CC=CC=C32)=CC=C1 MZYDBGLUVPLRKR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052735 hafnium Inorganic materials 0.000 claims description 15
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 claims description 15
- 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 14
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 claims description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 14
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 14
- 229910002115 bismuth titanate Inorganic materials 0.000 claims description 14
- XTUHPOUJWWTMNC-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)chromium Chemical compound [Co+2].[O-][Cr]([O-])(=O)=O XTUHPOUJWWTMNC-UHFFFAOYSA-N 0.000 claims description 14
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 14
- GUZVXPBOEVZXAC-UHFFFAOYSA-N iron lutetium Chemical compound [Fe].[Fe].[Lu] GUZVXPBOEVZXAC-UHFFFAOYSA-N 0.000 claims description 14
- QGAXAFUJMMYEPE-UHFFFAOYSA-N nickel chromate Chemical compound [Ni+2].[O-][Cr]([O-])(=O)=O QGAXAFUJMMYEPE-UHFFFAOYSA-N 0.000 claims description 14
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 14
- 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 14
- 229910052582 BN Inorganic materials 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 12
- 239000007983 Tris buffer Substances 0.000 claims description 12
- ZSUIPMIFNOUPEF-UHFFFAOYSA-N 3-(3-tert-butylphenyl)-5-phenyl-1h-1,2,4-triazole Chemical compound CC(C)(C)C1=CC=CC(C=2N=C(NN=2)C=2C=CC=CC=2)=C1 ZSUIPMIFNOUPEF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052797 bismuth Inorganic materials 0.000 claims description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 7
- HWJHZLJIIWOTGZ-UHFFFAOYSA-N n-(hydroxymethyl)acetamide Chemical compound CC(=O)NCO HWJHZLJIIWOTGZ-UHFFFAOYSA-N 0.000 claims description 7
- MRPWWVMHWSDJEH-UHFFFAOYSA-N antimony telluride Chemical group [SbH3+3].[SbH3+3].[TeH2-2].[TeH2-2].[TeH2-2] MRPWWVMHWSDJEH-UHFFFAOYSA-N 0.000 claims description 5
- WYUZTTNXJUJWQQ-UHFFFAOYSA-N tin telluride Chemical compound [Te]=[Sn] WYUZTTNXJUJWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 abstract description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 43
- 238000001704 evaporation Methods 0.000 description 30
- 230000008020 evaporation Effects 0.000 description 26
- 238000002347 injection Methods 0.000 description 25
- 239000007924 injection Substances 0.000 description 25
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical group [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 24
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 12
- HNWFFTUWRIGBNM-UHFFFAOYSA-N 2-methyl-9,10-dinaphthalen-2-ylanthracene Chemical compound C1=CC=CC2=CC(C3=C4C=CC=CC4=C(C=4C=C5C=CC=CC5=CC=4)C4=CC=C(C=C43)C)=CC=C21 HNWFFTUWRIGBNM-UHFFFAOYSA-N 0.000 description 12
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound 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 description 12
- 239000010952 cobalt-chrome Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- AYTVLULEEPNWAX-UHFFFAOYSA-N cesium;azide Chemical group [Cs+].[N-]=[N+]=[N-] AYTVLULEEPNWAX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910002665 PbTe Inorganic materials 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 6
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 6
- 229910020068 MgAl Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 5
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound 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 description 5
- 239000000075 oxide glass Substances 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 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 description 3
- UURRKPRQEQXTBB-UHFFFAOYSA-N tellanylidenestannane Chemical compound [Te]=[SnH2] UURRKPRQEQXTBB-UHFFFAOYSA-N 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 3
- DCORZIJYLAVAQJ-UHFFFAOYSA-N N1N=CN=C1.C1(=CC=CC=C1)C1=CC=CC(=C1)C(C)(C)C Chemical compound N1N=CN=C1.C1(=CC=CC=C1)C1=CC=CC(=C1)C(C)(C)C DCORZIJYLAVAQJ-UHFFFAOYSA-N 0.000 description 2
- 229910017629 Sb2Te3 Inorganic materials 0.000 description 2
- 229910005642 SnTe Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 210000001072 colon Anatomy 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007666 vacuum forming 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
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/841—Self-supporting sealing arrangements
-
- 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
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
- H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
-
- 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
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to an organic light-emitting diode device and a packaging method thereof. The organic light-emitting diode device comprises an anode conductive substrate, a light-emitting functional layer, a cathode and a packaging cover, wherein the light-emitting functional layer and the cathode are sequentially stacked on the anode conductive substrate, the packaging cover packages the light-emitting functional layer and the cathode on the anode conductive substrate and comprises a first organic barrier layer, a first inorganic barrier layer, a second organic barrier layer and a second inorganic barrier layer which sequentially cover the organic light-emitting functional layer and the cathode. Materials of the first organic barrier layer include a first hole transmission material and a first electron transmission material, materials of the first inorganic barrier layer include a telluride, a first nitride and a first alloy oxide, materials of the second organic barrier layer include a second hole transmission material and a second electron transmission material, and materials of the second inorganic barrier layer include a second nitride and a second alloy oxide. The service life of the organic light-emitting diode device is long.
Description
Technical Field
The invention relates to the technical field of electroluminescence, in particular to an organic electroluminescence device and a packaging method thereof.
Background
Organic electroluminescent devices (OLEDs) are a class of current-mode semiconductor light-emitting devices based on organic materials. The typical structure is that a layer of organic luminescent material with the thickness of dozens of nanometers is made on ITO glass to be used as a luminescent layer, and a layer of metal electrode with low work function is arranged above the luminescent layer. When a voltage is applied across the electrodes, the light-emitting layer generates light radiation.
The OLED device has the advantages of active light emission, high light emitting efficiency, low power consumption, lightness, thinness, no viewing angle limitation, and the like, and is considered by the industry as a new generation device which is most likely to occupy an dominating position in the future illumination and display device market. As a new lighting and display technology, OLED technology has developed rapidly over the last decade, with great success. As more and more illumination and display manufacturers are increasingly invested in research and development in the world, the industrialization process of the OLED is greatly promoted, so that the growth speed of the OLED industry is remarkable, and the day before large-scale mass production is reached.
However, the light emitting layer in the OLED is very sensitive to pollutants, oxygen, water vapor, etc. in the atmosphere, and a chemical reaction occurs under the action of the pollutants, oxygen, water vapor, etc. to reduce the luminous quantum efficiency, while the cathode is generally formed of an active metal and is easily corroded in air or oxygen, thereby resulting in poor stability and short service life of the OLED.
Disclosure of Invention
Based on this, it is necessary to provide an organic electroluminescent device having a long lifetime.
Further, an encapsulation method of the organic electroluminescent device is provided.
An organic electroluminescent device comprises an anode conductive substrate, a light-emitting functional layer, a cathode and a packaging cover, wherein the light-emitting functional layer and the cathode are sequentially stacked on the anode conductive substrate, the light-emitting functional layer and the cathode are packaged on the anode conductive substrate by the packaging cover, and the packaging cover comprises a first organic barrier layer, a first inorganic barrier layer, a second organic barrier layer and a second inorganic barrier layer which are sequentially covered on the organic light-emitting functional layer and the cathode; wherein,
the material of the first organic barrier layer includes a first hole transporting material which is N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-biphenyldiamine, N' -bis (α -naphthyl) -N, N '-diphenyl-4, 4' -diamine, 1-bis ((4-N, N '-bis (p-tolyl) amine) phenyl) cyclohexane, 2-methyl-9, 10-bis (imidazol-2-yl) anthracene, 4',4 "-tris (carbazol-9-yl) triphenylamine, or 1, 3-bis (9H-carbazol-9-yl) benzene, and a first electron transporting material which is 4, 7-diphenylphenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 8-hydroxyquinolinoaluminum, bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum, or 3- (4-biphenyl) -4-phenyl-5-tert-butyl-phenyl-1, 2, 4-triazole;
the material of the first inorganic barrier layer comprises telluride, first nitride and first alloy oxide, wherein the telluride is antimony telluride, bismuth telluride, cadmium telluride, indium telluride, tin telluride or lead telluride, the first nitride is silicon nitride, aluminum nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, and the first alloy oxide is magnesium metaaluminate, bismuth titanate, nickel chromate, cobalt chromate, iron lutetium or yttrium aluminate;
the material of the second organic barrier layer includes a second hole transporting material and a second electron transporting material, the second hole transporting material is N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-biphenyldiamine, N' -bis (α -naphthyl) -N, N '-diphenyl-4, 4' -diamine, 1-bis ((4-N, N '-bis (p-tolyl) amine) phenyl) cyclohexane, 2-methyl-9, 10-bis (imidazol-2-yl) anthracene, 4',4 ″ -tris (carbazol-9-yl) triphenylamine, or 1, 3-bis (9H-carbazol-9-yl) benzene, the second electron transporting material is 4, 7-diphenylphenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 8-hydroxyquinolinoaluminum, bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum or 3- (4-biphenyl) -4-phenyl-5-tert-butylbenzene-1, 2, 4-triazole;
the material of the second inorganic barrier layer comprises a second nitride and a second alloy oxide, the second nitride is silicon nitride, aluminum nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, and the second alloy oxide is magnesium metaaluminate, bismuth titanate, nickel chromate, cobalt chromate, iron lutetium or yttrium aluminate.
In one embodiment, the number of the packaging covers is 3-5, and the 3-5 packaging covers are sequentially covered on the light-emitting function layer and the cathode.
In one embodiment, the molar ratio of the first hole transport material to the first electron transport material is 40:100 to 60: 100.
In one embodiment, in the first inorganic barrier layer, the mass percentage of the first nitride is 10% to 40%, and the mass percentage of the first alloy oxide is 10% to 30%.
In one embodiment, the molar ratio of the second hole transport material to the second electron transport material is 40:100 to 60: 100.
In one embodiment, the second nitride accounts for 10% to 40% of the second inorganic barrier layer by mass.
In one embodiment, the first organic barrier layer and the second organic barrier layer have a thickness of 200 nm to 300 nm.
In one embodiment, the first inorganic barrier layer and the second inorganic barrier layer have a thickness of 100 nm to 200 nm.
A packaging method of an organic electroluminescent device comprises the following steps:
providing an anode conductive substrate, and forming a light-emitting functional layer on the anode conductive substrate through vacuum evaporation;
forming a cathode on the light-emitting functional layer by vacuum evaporation;
preparing a first organic barrier layer by vacuum evaporation, wherein the first organic barrier layer is arranged on the anode conductive substrate and covers the light-emitting functional layer and the cathode, the materials of the first organic barrier layer comprise a first hole transport material and a first electron transport material, the first hole transport material is N, N '-diphenyl-N, N' -di (3-methylphenyl) -4,4 '-biphenyldiamine, N' -di (alpha-naphthyl) -N, N '-diphenyl-4, 4' -diamine, 1-di ((4-N, N '-di (p-tolyl) amine) phenyl) cyclohexane, 2-methyl-9, 10-di (imidazol-2-yl) anthracene, 4',4'' -tri (carbazol-9-yl) triphenylamine or 1, 3-bis (9H-carbazol-9-yl) benzene, the first electron transport material being 4, 7-diphenylphenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 8-hydroxyquinoline aluminum, bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum, or 3- (4-biphenyl) -4 phenyl-5-tert-butyl-phenyl-1, 2, 4-triazole;
preparing a first inorganic barrier layer by magnetron sputtering, wherein the first inorganic barrier layer is arranged on the anode conductive substrate and covers the first organic barrier layer, the first inorganic barrier layer is made of telluride, a first nitride and a first alloy oxide, the telluride is antimony telluride, bismuth telluride, cadmium telluride, indium telluride, tin telluride or lead telluride, the first nitride is silicon nitride, aluminum nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, and the first alloy oxide is magnesium metaaluminate, bismuth titanate, nickel chromate, cobalt chromate, iron lutetium or yttrium aluminate;
preparing a second organic barrier layer by vacuum evaporation, wherein the second organic barrier layer is arranged on the anode conductive substrate and covers the first inorganic barrier layer, the material of the second organic barrier layer comprises a second hole transport material and a second electron transport material, the second hole transport material is N, N '-diphenyl-N, N' -di (3-methylphenyl) -4,4 '-biphenyldiamine, N' -di (alpha-naphthyl) -N, N '-diphenyl-4, 4' -diamine, 1-di ((4-N, N '-di (p-tolyl) amine) phenyl) cyclohexane, 2-methyl-9, 10-di (imidazol-2-yl) anthracene, 4',4'' -tri (carbazol-9-yl) triphenylamine or 1, 3-bis (9H-carbazol-9-yl) benzene, the second electron transport material being 4, 7-diphenylphenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 8-hydroxyquinoline aluminum, bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum, or 3- (4-biphenyl) -4 phenyl-5-tert-butyl-phenyl-1, 2, 4-triazole; and
preparing a second inorganic barrier layer by magnetron sputtering, wherein the second inorganic barrier layer is arranged on the anode conductive substrate and covers the second organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are sequentially covered on the light-emitting function layer and the cathode to form a packaging cover arranged on the anode conductive substrate, and the packaging cover is packaged to obtain the organic electroluminescent device; the material of the second inorganic barrier layer comprises a second nitride and a second alloy oxide, wherein the second nitride is silicon nitride, aluminum nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, and the second alloy oxide is magnesium metaaluminate, bismuth titanate, nickel chromate, cobalt chromate, iron lutetium or yttrium aluminate.
In one embodiment, in the step of preparing the first organic barrier layer by vacuum evaporation and the step of preparing the second organic barrier layer by vacuum evaporation, the vacuum degree of the vacuum evaporation is 1 × 10-5Pa～1×10-3Pa；
In the step of preparing the first inorganic barrier layer by magnetron sputtering and the step of preparing the second inorganic barrier layer by magnetron sputtering, the vacuum degree of the background is 1 multiplied by 10-5Pa～1×10-3Pa。
The anode conductive substrate of the organic electroluminescent device is provided with the packaging cover, the active light-emitting functional layer and the active cathode are packaged on the anode conductive substrate by the packaging cover, the first organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are sequentially covered on the light-emitting functional layer and the anode to form the compact packaging cover, the erosion of active substances such as external water, oxygen and the like to the light-emitting functional layer and the cathode can be effectively reduced, the light-emitting functional layer and the cathode of the organic electroluminescent device are effectively protected, and therefore the service life of the organic electroluminescent device is prolonged.
Drawings
Fig. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment;
fig. 2 is a flowchart of an organic electroluminescent device packaging method according to an embodiment.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Referring to fig. 1, an organic electroluminescent device 100 according to an embodiment includes an anode conductive substrate 10, a light-emitting functional layer 20, a cathode 30, and a package cover 40.
The light emitting functional layer 20 and the cathode 30 are sequentially laminated on the anode conductive substrate 10. The light-emitting functional layer 20 covers part of the surface of the anode conductive substrate 10, the encapsulation cover 40 is disposed on the surface of the anode conductive substrate 10 not covered by the light-emitting functional layer 20 and covers the light-emitting functional layer 20 and the cathode 30, and the light-emitting functional layer 20 and the cathode 30 are encapsulated on the anode conductive substrate 10.
The anode conductive substrate 10 is indium tin oxide glass (ITO), aluminum zinc oxide glass (AZO), or indium zinc oxide glass (IZO), and preferably indium tin oxide glass (ITO).
The light emitting function layer 20 includes a hole injection layer (not shown), a hole transport layer (not shown), a light emitting layer (not shown), an electron transport layer (not shown), and an electron injection layer (not shown) sequentially stacked on the anode conductive substrate 10.
The material of the hole injection layer is molybdenum trioxide (MoO)3) Doped materials formed in N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB). Wherein, molybdenum trioxide (MoO)3) The mass ratio to N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was 30: 100.
Preferably, the hole injection layer has a thickness of 10 nm.
The material of the hole transport layer is 4,4',4' ' -tris (carbazol-9-yl) triphenylamine (TCTA).
Preferably, the hole transport layer has a thickness of 30 nm.
The material of the light-emitting layer is tris (2-phenylpyridine) iridium (Ir (ppy)3) Doped materials formed by doping 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI). Wherein, tris (2-phenylpyridine) iridium (Ir (ppy)3) The mass ratio to 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI) is 5: 100.
Preferably, the thickness of the light emitting layer is 20 nm.
The material of the electron transport layer is 4, 7-diphenyl-1, 10-phenanthroline (Bphen).
Preferably, the thickness of the electron transport layer is 10 nm.
The material of the electron injection layer is cesium azide (CsN)3) Doped material formed by doping in 4, 7-diphenyl-1, 10-phenanthroline (Bphen). Wherein, cesium azide (CsN)3) The mass ratio of the 4, 7-diphenyl-1, 10-phenanthroline (Bphen) to the total amount of the organic acid is 30: 100.
Preferably, the thickness of the electron injection layer is 20 nm.
The material of the cathode is metallic aluminum (Al). Preferably, the thickness of the cathode 30 is 100 nanometers.
The encapsulation cover 40 includes a first organic barrier layer 41, a first inorganic barrier layer 42, a second organic barrier layer 43, and a second inorganic barrier layer 44 sequentially covering the light emitting function layer 20 and the cathode 30.
The material of the first organic blocking layer 41 includes a first hole transport material and a first electron transport material.
The first hole transport material is N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-biphenyldiamine (TPD), N' -bis (α -naphthyl) -N, N '-diphenyl-4, 4' -diamine (NPB), 1-bis ((4-N, N '-bis (p-Tolyl) Amine) Phenyl) Cyclohexane (TAPC), 2-methyl-9, 10-bis (imidazol-2-yl) anthracene (MADN), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), or 1, 3-bis (9H-carbazol-9-yl) benzene (mCP).
The first electron transport material is 4, 7-diphenyl phenanthroline (Bpen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI), 8-hydroxyquinoline aluminum (Alq)3) Bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum (Balq) or 3- (4-biphenyl) -4 phenyl-5-tert-butyl-phenyl-1, 2, 4-Triazole (TAZ).
Preferably, the molar ratio of the first hole transport material to the first electron transport material is 40:100 to 60: 100.
Preferably, the thickness of the first organic barrier layer 41 is 200 nm to 300 nm.
The material of the first inorganic barrier layer 42 includes telluride, a first nitride, and a first alloy oxide.
The telluride is antimony tristelluride (Sb)2Te3) Bismuth telluride (Bi)2Te), cadmium telluride (CdTe), indium telluride (In)2Te3) Tin telluride (SnTe) or lead telluride (PbTe).
The first nitride is silicon nitride (Si)3N4) Aluminum nitride (AlN), Boron Nitride (BN), hafnium nitride (HfN), tantalum nitride (TaN), or titanium nitride (TiN).
The first alloy oxide is magnesium metaaluminate (MgAl)2O4) Bismuth titanate (Bi)2Ti4O11) Nickel chromate (CrNiO)4) Cobalt chromate (CoCr)2O4) Iron lutetium (Fe)2LuO4) Or yttrium aluminate (Y)3Al5O12）。
Preferably, in the first inorganic barrier layer 42, the mass percentage of the first nitride is 10% to 40%, and the mass percentage of the first alloy oxide is 10% to 30%.
Preferably, the thickness of the first inorganic barrier layer 42 is 100 nm to 200 nm.
The material of the second organic blocking layer 43 includes a second hole transport material and a second electron transport material.
The second hole transport material is N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-biphenyldiamine (TPD), N' -bis (α -naphthyl) -N, N '-diphenyl-4, 4' -diamine (NPB), 1-bis ((4-N, N '-bis (p-Tolyl) Amine) Phenyl) Cyclohexane (TAPC), 2-methyl-9, 10-bis (imidazol-2-yl) anthracene (MADN), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), or 1, 3-bis (9H-carbazol-9-yl) benzene (mCP).
The second electron transport material is 4, 7-diphenyl phenanthroline (Bphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI), 8-hydroxyquinoline aluminum (Alq)3) Bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum (Balq) or 3- (4-biphenyl) -4 phenyl-5-tert-butyl-phenyl-1, 2, 4-Triazole (TAZ).
Preferably, the molar ratio of the second hole transport material to the second electron transport material is 40:100 to 60: 100.
Preferably, the thickness of the second organic barrier layer 43 is 200 nm to 300 nm.
The material of the second inorganic barrier layer 44 includes a second nitride and a second alloy oxide.
The second nitride being silicon nitride (Si)3N4) Aluminum nitride (AlN), Boron Nitride (BN), hafnium nitride (HfN), tantalum nitride (TaN), or titanium nitride (TiN).
The second alloy oxide is magnesium metaaluminate (MgAl)2O4) Bismuth titanate (Bi)2Ti4O11) Nickel chromate (CrNiO)4) Cobalt chromate (CoCr)2O4) Iron lutetium (Fe)2LuO4) Or yttrium aluminate (Y)3Al5O12）。
Preferably, the second nitride accounts for 10% to 40% by mass of the second inorganic barrier layer 44.
The encapsulation cover 40 is disposed on the anode conductive substrate 10, and forms a sealed receiving cavity (not shown) with the anode conductive substrate 10, and the light-emitting functional layer 20 and the cathode 30 are received in the receiving cavity. The anode conductive substrate 10 has better barrier property, and the encapsulation cover 40 formed by the materials has higher compactness and can effectively block airFurther meets the sealing requirement of the package, thereby effectively protecting the light-emitting functional layer 20 and the cathode 30, and prolonging the service life of the organic electroluminescent device 100 (T701000 cd/m)2) Higher, up to 7600 hours or more.
Preferably, the number of the encapsulation covers 40 is 3 to 5. The 3-5 encapsulation covers 40 have different sizes, and the 3-5 encapsulation covers 40 with different sizes are sequentially covered on the light-emitting functional layer and the cathode in the order from small to large. 3-5 encapsulation covers 40 can further improve the sealing performance of the encapsulation and prolong the service life of the organic electroluminescent device 100.
Referring to fig. 2, a method for encapsulating an organic electroluminescent device according to an embodiment includes the following steps:
step S110: providing an anode conductive substrate, and forming a light-emitting functional layer on the anode conductive substrate by vacuum evaporation.
The anode conductive substrate is indium tin oxide glass (ITO), aluminum zinc oxide glass (AZO), or indium zinc oxide glass (IZO), and preferably indium tin oxide glass (ITO).
And (3) evaporating indium tin oxide, aluminum zinc oxide or indium zinc oxide on the clean and dry glass substrate by adopting vacuum evaporation, and forming an anode pattern on the glass substrate to obtain the anode conductive substrate.
Preferably, the thickness of the anode pattern is 100 nm.
Before a light-emitting functional layer is formed on an anode conductive substrate by vacuum evaporation, the anode conductive substrate is firstly sequentially placed into acetone, ethanol, deionized water and ethanol for ultrasonic cleaning, each ultrasonic cleaning is carried out for 5 minutes, then nitrogen is used for blow-drying, and then an oven is used for drying, so that the clean and dry anode conductive substrate is obtained. And further carrying out surface activity treatment on the anode conductive substrate to increase the oxygen content on the surface of the anode conductive substrate and improve the work function of the anode conductive substrate. The step of performing surface active treatment is to treat the cleaned and dried anode conductive substrate for 30-50 minutes by using ultraviolet-ozone (UV-ozone).
The light-emitting function layer comprises a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and an electron injection layer which are sequentially stacked on the anode conductive substrate. The light-emitting functional layer covers part of the surface of the anode conductive substrate.
And sequentially forming a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer and an electron injection layer on the clean and dry anode conductive substrate by vacuum evaporation to obtain a luminescent functional layer laminated on the anode conductive substrate.
The material of the hole injection layer is molybdenum trioxide (MoO)3) Doped materials formed in N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB). Wherein, molybdenum trioxide (MoO)3) The mass ratio to N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) was 30: 100.
Preferably, the hole injection layer has a thickness of 10 nm.
The vacuum degree of the hole injection layer formed by vacuum evaporation was 3X 10-5Pa. Evaporation rate of
The material of the hole transport layer is 4,4',4' ' -tris (carbazol-9-yl) triphenylamine (TCTA).
Preferably, the hole transport layer has a thickness of 30 nm.
The vacuum degree of the hole transport layer formed by vacuum evaporation was 3X 10-5Pa. Evaporation rate of
The material of the light-emitting layer is tris (2-phenylpyridine) iridium (Ir (ppy)3) Doped materials formed by doping 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI). Wherein,tris (2-phenylpyridine) iridium (Ir (ppy)3) The mass ratio to 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI) is 5: 100.
Preferably, the thickness of the light emitting layer is 20 nm.
The vacuum degree of the luminescent layer formed by vacuum evaporation is 3 × 10-5Pa. Evaporation rate of
The material of the electron transport layer is 4, 7-diphenyl-1, 10-phenanthroline (Bphen)
Preferably, the thickness of the electron transport layer is 10 nm.
The vacuum degree of the electron transmission layer formed by vacuum evaporation is 3 multiplied by 10-5Pa. Evaporation rate of
The material of the electron injection layer is cesium azide (CsN)3) Doped material formed by doping in 4, 7-diphenyl-1, 10-phenanthroline (Bphen). Wherein, cesium azide (CsN)3) The mass ratio of the 4, 7-diphenyl-1, 10-phenanthroline (Bphen) to the total amount of the organic acid is 30: 100.
Preferably, the thickness of the electron injection layer is 20 nm.
The vacuum degree of the electron injection layer formed by vacuum evaporation is 3X 10-5Pa. Evaporation rate of
Step S120: and forming a cathode on the light-emitting functional layer by vacuum evaporation.
The material of the cathode is metallic aluminum (Al). Preferably, the cathode has a thickness of 100 nm.
The vacuum degree of vacuum deposition is 3X 10-5Pa. Speed of evaporationDegree of
Step S130: and preparing a first organic barrier layer by vacuum evaporation, wherein the first organic barrier layer is arranged on the anode conductive substrate and covers the light-emitting functional layer and the cathode.
The material of the first organic barrier layer includes a first hole transport material and a first electron transport material.
The first hole transport material is N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-biphenyldiamine (TPD), N' -bis (α -naphthyl) -N, N '-diphenyl-4, 4' -diamine (NPB), 1-bis ((4-N, N '-bis (p-Tolyl) Amine) Phenyl) Cyclohexane (TAPC), 2-methyl-9, 10-bis (imidazol-2-yl) anthracene (MADN), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), or 1, 3-bis (9H-carbazol-9-yl) benzene (mCP).
The first electron transport material is 4, 7-diphenyl phenanthroline (Bphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI), 8-hydroxyquinoline aluminum (Alq 3), bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum (Balq), or 3- (4-biphenyl) -4-phenyl-5-tert-butyl-benzene-1, 2, 4-Triazole (TAZ).
Preferably, the molar ratio of the first hole transport material to the first electron transport material is 40:100 to 60: 100.
Preferably, the thickness of the first organic barrier layer is 200 nm to 300 nm.
The degree of vacuum deposition was 1X 10-5Pa～1×10-3Pa. Evaporation rate of
Step S140: and preparing a first inorganic barrier layer by magnetron sputtering, wherein the first inorganic barrier layer is arranged on the anode conductive substrate and covers the first organic barrier layer.
The material of the first inorganic barrier layer includes telluride, a first nitride and a first alloy oxide.
The telluride is antimony tristelluride (Sb)2Te3) Bismuth telluride (Bi)2Te), cadmium telluride (CdTe), indium telluride (In)2Te3) Tin telluride (SnTe) or lead telluride (PbTe).
The first nitride is silicon nitride (Si)3N4) Aluminum nitride (AlN), Boron Nitride (BN), hafnium nitride (HfN), tantalum nitride (TaN), or titanium nitride (TiN).
The first alloy oxide is magnesium metaaluminate (MgAl)2O4) Bismuth titanate (Bi)2Ti4O11) Nickel chromate (CrNiO)4) Cobalt chromate (CoCr)2O4) Iron lutetium (Fe)2LuO4) Or yttrium aluminate (Y)3Al5O12）。
Preferably, in the first inorganic barrier layer, the mass percentage of the first nitride is 10% to 40%, and the mass percentage of the first alloy oxide is 10% to 30%.
Preferably, the thickness of the first inorganic barrier layer is 100 nm to 200 nm.
Background vacuum degree of 1X 10-5Pa～1×10-3Pa。
Step S150: and preparing a second organic barrier layer by vacuum evaporation, wherein the second organic barrier layer is arranged on the anode conductive substrate and covers the first inorganic barrier layer.
The material of the second organic blocking layer includes a second hole transport material and a second electron transport material.
The second hole transport material is N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-biphenyldiamine (TPD), N' -bis (α -naphthyl) -N, N '-diphenyl-4, 4' -diamine (NPB), 1-bis ((4-N, N '-bis (p-Tolyl) Amine) Phenyl) Cyclohexane (TAPC), 2-methyl-9, 10-bis (imidazol-2-yl) anthracene (MADN), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), or 1, 3-bis (9H-carbazol-9-yl) benzene (mCP).
The second electron transport material is 4, 7-diphenyl phenanthroline (Bphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBI), 8-hydroxyquinoline aluminum (Alq)3) Bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum (Balq) or 3- (4-biphenyl) -4 phenyl-5-tert-butyl-phenyl-1, 2, 4-Triazole (TAZ).
Preferably, the molar ratio of the second hole transport material to the second electron transport material is 40:100 to 60: 100.
Preferably, the thickness of the second organic barrier layer is 200 nm to 300 nm.
The degree of vacuum deposition was 1X 10-5Pa～1×10-3Pa. Evaporation rate of
Step S160: and preparing a second inorganic barrier layer by magnetron sputtering, wherein the second inorganic barrier layer is arranged on the anode conductive substrate and covers the second organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are sequentially covered on the light-emitting function layer and the cathode to form a packaging cover arranged on the anode conductive substrate, and the packaging cover is packaged to obtain the organic electroluminescent device.
The material of the second inorganic barrier layer includes a second nitride and a second alloy oxide.
The second nitride being silicon nitride (Si)3N4) Aluminum nitride (AlN), Boron Nitride (BN), hafnium nitride (HfN), tantalum nitride (TaN), or titanium nitride (TiN).
The second alloy oxide is meta-aluminumMagnesium (MgAl)2O4) Bismuth titanate (Bi)2Ti4O11) Nickel chromate (CrNiO)4) Cobalt chromate (CoCr)2O4) Iron lutetium (Fe)2LuO4) Or yttrium aluminate (Y)3Al5O12）。
Preferably, the second nitride accounts for 10% to 40% of the second inorganic barrier layer by mass.
Background vacuum degree of 1X 10-5Pa～1×10-3Pa。
And the first organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are sequentially covered on the light-emitting functional layer and the cathode to form a packaging cover arranged on the anode conductive substrate, and the light-emitting functional layer and the cathode are packaged on the anode conductive substrate by the packaging cover to obtain the organic electroluminescent device through packaging.
The packaging method of the organic electroluminescent device adopts the vacuum evaporation and magnetron sputtering method to form the packaging cover which covers the organic light-emitting functional layer and the cathode, so that the light-emitting functional layer and the cathode are packaged on the anode conductive substrate, the light-emitting functional layer and the cathode can be well protected, the organic electroluminescent device with higher stability and longer service life can be obtained by packaging, the packaging process is simple, and the large-scale packaging is easy.
It is understood that, in other embodiments, when the number of the encapsulation covers is 3 to 5, the steps S130, S140, S150 and S1602 to 4 are alternately repeated to form 3 to 5 encapsulation covers sequentially covering the organic light emitting function layer and the cathode.
At a vacuum degree of 1X 10-5Pa～1×10-3Pa, at an evaporation rate ofForming a first organic barrier layer and a second organic barrier layer by vacuum evaporation, and obtaining a background vacuum degree of 1 × 10-5Pa～1×10-3Forming a first inorganic barrier layer and a second inorganic barrier layer by magnetron sputtering under Pa, which is beneficial to forming a compact and flawless film layer and obtaining a packaging cover with higher compactness.
The following are specific examples.
Example 1
The structure is ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/TPD:Bphen/Sb2Te3:Si3N4:MgAl2O4/TPD:Bphen/Si3N4:MgAl2O4The encapsulation of the organic electroluminescent device of (1).
(1) An anode conductive substrate is provided, which is indium tin oxide glass, denoted ITO. Firstly, the anode conductive substrate is sequentially placed into acetone, ethanol, deionized water and ethanol for ultrasonic cleaning, ultrasonic cleaning is carried out for 5 minutes each time, then nitrogen is used for blow-drying, and then an oven is used for drying, so that the clean and dry anode conductive substrate is obtained. Further adopting ultraviolet-ozone (UV-ozone) to treat the cleaned and dried anode conductive substrate for surface active treatment for 30 minutes so as to increase the oxygen content of the surface of the anode conductive substrate and improve the work function of the anode conductive substrate;
(2) a hole injection layer formed on the surface of the anode conductive substrate by vacuum evaporation with a vacuum degree of 3 × 10-5Pa, evaporation rate ofThe material of the hole injection layer is molybdenum trioxide (MoO)3) Doped material formed in N, N '-diphenyl-N, N' -di (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), denoted MoO3NPB, wherein MoO3The mass ratio of the NPB to the NPB is 30: 100; the thickness of the hole injection layer is 10 nm;
(3) vacuum vapor-depositing voids on the surface of the hole injection layerA hole transfer layer, vacuum evaporation coating with vacuum degree of 3 × 10-5Pa, evaporation rate ofThe material of the hole transport layer is 4,4',4' ' -tri (carbazole-9-yl) triphenylamine (TCTA); the thickness of the hole transport layer is 30 nm;
(4) vacuum evaporating to form a luminescent layer on the hole transport layer with vacuum degree of 5 × 10-5Pa, evaporation rate ofThe material of the light-emitting layer is tris (2-phenylpyridine) iridium (Ir (ppy)3) Doped materials formed in 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI) and designated Ir (ppy)3TPBI, wherein Ir (ppy)3) The mass ratio of TPBI to TPBI is 5: 100; the thickness of the light-emitting layer is 20 nanometers;
(5) vacuum evaporating to form electron transport layer on the luminescent layer with vacuum degree of 3 × 10-5Pa, evaporation rate ofThe material of the electron transport layer is 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the thickness of the electron transport layer is 10 nanometers;
(6) vacuum evaporating the electron transport layer to form an electron injection layer with a vacuum degree of 3 × 10-5Pa, evaporation rate ofThe material of the electron injection layer is cesium azide (CsN)3) Doped material formed by doping 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and expressed as CsN3Bphen, wherein CsN3The mass ratio of the Bphen to the Bphen is 30: 100; the thickness of the electron injection layer is 20 nanometers; a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are sequentially stacked on the anode conductive substrateA light-emitting functional energy layer;
(7) forming a cathode on the light-emitting functional layer by vacuum evaporation with a vacuum degree of 3 × 10-5Pa, evaporation rate ofThe cathode is made of aluminum, and the thickness of the cathode is 100 nanometers;
(8) preparing a first organic barrier layer on the anode conductive substrate and covering the light-emitting functional layer and the cathode by vacuum evaporation with vacuum degree of 1 × 10-5Pa, evaporation rate ofThe material of the first organic barrier layer comprises N, N ' -diphenyl-N, N ' -di (3-methylphenyl) -4,4' -diphenyldiamine (TPD) and 4, 7-diphenyl phenanthroline (Bphen), wherein the molar ratio of TPD to Bphen is 55:100, and the thickness of the first organic barrier layer is 300 nanometers;
(9) preparing a first inorganic barrier layer by magnetron sputtering, wherein the first inorganic barrier layer is arranged on the anode conductive substrate and covered on the first organic barrier layer, and the background vacuum degree is 1 multiplied by 10-5Pa, the material of the first inorganic barrier layer comprises antimony telluride (Sb)2Te3) Silicon nitride (Si)3N4) And magnesium metaaluminate (MgAl)2O4) In the first inorganic barrier layer, Si3N440% by mass of MgAl2O4The mass percentage content of the compound is 12 percent; the thickness of the first inorganic barrier layer is 200 nanometers;
(10) preparing a second organic barrier layer on the anode conductive substrate and covering the first inorganic barrier layer by vacuum evaporation with vacuum degree of 1 × 10-5Pa, evaporation rate ofThe material of the second organic barrier layer comprises N, N' -diphenyl-N, N ' -bis (3-methylphenyl) -4,4' -biphenyldiamine (TPD) and 4, 7-diphenyl phenanthroline (Bphen), wherein the molar ratio of TPD to Bphen is 55:100, and the thickness of the second organic barrier layer is 300 nm;
(11) preparing a second inorganic barrier layer by magnetron sputtering, wherein the second inorganic barrier layer is arranged on the anode conductive substrate and covered on the second organic barrier layer, and the background vacuum degree is 1 × 10-5Pa, the material of the second inorganic barrier layer comprises silicon nitride (Si)3N4) And magnesium metaaluminate (MgAl)2O4) Wherein Si is3N4The mass percentage of the second inorganic barrier layer is 40%; the thickness of the second inorganic barrier layer is 200 nm;
a first organic barrier layer, a first inorganic barrier layer, a second organic barrier layer and a second inorganic barrier layer are sequentially covered on the light-emitting function layer and the cathode to form a packaging cover arranged on the anode conductive substrate, and the packaging structure is ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/TPD:Bphen/Sb2Te3:Si3N4:MgAl2O4/TPD:Bphen/Si3N4:MgAl2O4The organic electroluminescent device of (1). Wherein, the diagonal bar "/" represents lamination or covering, the colon ": represents doping or mixing, the same below.
Example 2
The structure is ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/NPB:BCP/Bi2Te:AlN:Bi2Ti4O11/NPB:BCP/BN:Bi2Ti4O11The encapsulation of the organic electroluminescent device of (1).
(1) Examples (7) to (7) are the same as example 1.
(8) Preparing a first organic barrier layer by vacuum evaporation, wherein the first organic barrier layer is arranged on the anode conductive substrateAnd covering the luminescent functional layer and the cathode, wherein the vacuum degree of vacuum evaporation is 5 × 10-5Pa, evaporation rate ofThe material of the first organic barrier layer comprises (N, N ' -di (alpha-naphthyl) -N, N ' -diphenyl-4, 4' -diamine (NPB) and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), wherein the molar ratio of NPB to BCP is 50:100, and the thickness of the first organic barrier layer is 250 nanometers;
(9) preparing a first inorganic barrier layer by magnetron sputtering, wherein the first inorganic barrier layer is arranged on the anode conductive substrate and covered on the first organic barrier layer, and the background vacuum degree is 1 multiplied by 10-5Pa, the material of the first inorganic barrier layer comprises bismuth telluride (Bi)2Te), aluminum nitride (AlN) and bismuth titanate (Bi)2Ti4O11) In the first inorganic barrier layer, the mass percentage of AlN is 10 percent, and Bi is2Ti4O11The mass percentage content of the compound is 30 percent; the thickness of the first inorganic barrier layer is 100 nanometers;
(10) preparing a second organic barrier layer on the anode conductive substrate and covering the first inorganic barrier layer by vacuum evaporation with vacuum degree of 5 × 10-5Pa, evaporation rate ofThe material of the second organic barrier layer comprises N, N ' -di (alpha-naphthyl) -N, N ' -diphenyl-4, 4' -diamine (NPB) and 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), wherein the molar ratio of NPB to BCP is 50:100, and the thickness of the second organic barrier layer is 250 nanometers;
(11) preparing a second inorganic barrier layer by magnetron sputtering, wherein the second inorganic barrier layer is arranged on the anode conductive substrate and covered on the second organic barrier layer, and the background vacuum degree is 1 × 10-5Pa, the material of the second inorganic barrier layer comprises Boron Nitride (BN) and bismuth titanate (Bi)2Ti4O11) WhereinBN accounts for 20 percent of the second inorganic barrier layer by mass; the thickness of the second inorganic barrier layer is 140 nm; the first organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are sequentially covered on the light-emitting function layer and the cathode to form a packaging cover arranged on the anode conductive substrate;
(12) alternately repeating the steps (8) to (11) for 4 times to form 5 packaging covers which are sequentially covered on the luminous functional layer and the cathode, and packaging to obtain the structure of ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/NPB:BCP/Bi2Te:AlN:Bi2Ti4O11/NPB:BCP/BN:Bi2Ti4O11The organic electroluminescent device of (1).
Example 3
The structure is ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/TAPC:TPBI/CdTe:BN:CrNiO4/TAPC:TPBI/AlN:CrNiO4The encapsulation of the organic electroluminescent device of (1).
(1) Examples (7) to (7) are the same as example 1.
(8) Preparing a first organic barrier layer on the anode conductive substrate and covering the light-emitting functional layer and the cathode by vacuum evaporation with vacuum degree of 5 × 10-5Pa, evaporation rate ofThe material of the first organic barrier layer comprises 1, 1-bis ((4-N, N' -di (p-Tolyl) Amine) Phenyl) Cyclohexane (TAPC) and 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI), wherein the molar ratio of TAPC to TPBI is 50:100, and the thickness of the first organic barrier layer is 200 nm;
(9) preparing a first inorganic barrier layer by magnetron sputtering, wherein the first inorganic barrier layer is arranged on the anode conductive substrateThe cover is arranged on the first organic barrier layer, and the vacuum degree of the background is 1 × 10-5Pa, the material of the first inorganic barrier layer comprises cadmium telluride (CdTe), Boron Nitride (BN) and nickel chromate (CrNiO)4) In the first inorganic barrier layer, the mass percent of BN is 30 percent, and CrNiO4The mass percentage content of the compound is 10 percent; the thickness of the first inorganic barrier layer is 150 nm;
(10) preparing a second organic barrier layer on the anode conductive substrate and covering the first inorganic barrier layer by vacuum evaporation with vacuum degree of 5 × 10-5Pa, evaporation rate ofThe material of the second organic barrier layer comprises 1, 1-bis ((4-N, N' -di (p-Tolyl) Amine) Phenyl) Cyclohexane (TAPC) and 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBI), wherein the molar ratio of TAPC to TPBI is 50:100, and the thickness of the second organic barrier layer is 200 nm;
(11) preparing a second inorganic barrier layer by magnetron sputtering, wherein the second inorganic barrier layer is arranged on the anode conductive substrate and covered on the second organic barrier layer, and the background vacuum degree is 1 × 10-4Pa, the material of the second inorganic barrier layer comprises aluminum nitride (AlN) and nickel chromate (CrNiO)4) Wherein the AlN accounts for 10 percent of the second inorganic barrier layer by mass; the thickness of the second inorganic barrier layer is 150 nm; the first organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are sequentially covered on the light-emitting function layer and the cathode to form a packaging cover arranged on the anode conductive substrate;
(12) alternately repeating the steps (8) to (11) for 4 times to form 5 packaging covers which are sequentially covered on the luminous functional layer and the cathode, and packaging to obtain the structure of ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/TAPC:TPBI/CdTe:BN:CrNiO4/TAPC:TPBI/AlN:CrNiO4The organic electroluminescent device of (1).
Example 4
The structure is ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/MADN:Alq3/In2Te3:HfN:CoCr2O4/MADN:Alq3/HfN:CoCr2O4The encapsulation of the organic electroluminescent device of (1).
(1) Examples (7) to (7) are the same as example 1.
(8) Preparing a first organic barrier layer on the anode conductive substrate and covering the light-emitting functional layer and the cathode by vacuum evaporation with vacuum degree of 5 × 10-5Pa, evaporation rate ofThe material of the first organic barrier layer includes 2-methyl-9, 10-bis (imidazol-2-yl) anthracene (MADN) and 8-hydroxyquinoline aluminum (Alq)3) Wherein, MADN and Alq3Is 60:100, the thickness of the first organic barrier layer is 250 nm;
(9) preparing a first inorganic barrier layer by magnetron sputtering, wherein the first inorganic barrier layer is arranged on the anode conductive substrate and covered on the first organic barrier layer, and the background vacuum degree is 5 multiplied by 10-5Pa, the material of the first inorganic barrier layer comprises indium telluride (In)2Te3) Hafnium nitride (HfN) and cobalt chromate (CoCr)2O4) In the first inorganic barrier layer, the mass percentage of hafnium nitride (HfN) is 20%, and CoCr2O4The mass percentage content of (A) is 18%; the thickness of the first inorganic barrier layer is 150 nm;
(10) preparing a second organic barrier layer on the anode conductive substrate and covering the first inorganic barrier layer by vacuum evaporation with vacuum degree of 5 × 10-5Pa, evaporation rate ofThe material of the second organic barrier layer includes 2-methyl-9, 10-bis (imidazol-2-yl) anthracene (MADN) and 8-hydroxyquinoline aluminum (Alq)3) Wherein, MADN and Alq3In a molar ratio of 60:100, the thickness of the second organic barrier layer is 250 nm;
(11) preparing a second inorganic barrier layer by magnetron sputtering, wherein the second inorganic barrier layer is arranged on the anode conductive substrate and covered on the second organic barrier layer, and the background vacuum degree is 1 × 10-4Pa, the material of the second inorganic barrier layer comprises hafnium nitride (HfN) and cobalt chromate (CoCr)2O4) Wherein the HfN accounts for 25% of the second inorganic barrier layer by mass; the thickness of the second inorganic barrier layer is 100 nanometers; the first organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are sequentially covered on the light-emitting function layer and the cathode to form a packaging cover arranged on the anode conductive substrate;
(12) alternately repeating the steps (8) to (11) for 4 times to form 5 packaging covers which are sequentially covered on the luminous functional layer and the cathode, and packaging to obtain the structure of ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/MADN:Alq3/In2Te3:HfN:CoCr2O4/MADN:Alq3/HfN:CoCr2O4The organic electroluminescent device of (1).
Example 5
The structure is ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/TCTA:Balq/SnTe:TaN:Fe2LuO4/TCTA:Balq/TaN:Fe2LuO4The encapsulation of the organic electroluminescent device of (1).
(1) Examples (7) to (7) are the same as example 1.
(8) Preparing a first organic barrier layer by vacuum evaporationThe layer is arranged on the anode conductive substrate and covers the light-emitting functional layer and the cathode, and the vacuum degree of vacuum evaporation is 5 multiplied by 10-5Pa, evaporation rate ofThe material of the first organic barrier layer comprises 4,4',4' ' -tris (carbazol-9-yl) triphenylamine (TCTA) and bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum (Balq), wherein the molar ratio of TCTA to Balq is 50:100, and the thickness of the first organic barrier layer is 250 nm;
(9) preparing a first inorganic barrier layer by magnetron sputtering, wherein the first inorganic barrier layer is arranged on the anode conductive substrate and covered on the first organic barrier layer, and the background vacuum degree is 5 multiplied by 10-5Pa, the material of the first inorganic barrier layer comprises tin telluride (SnTe), tantalum nitride (TaN) and iron lutetium (Fe)2LuO4) In the first inorganic barrier layer, the tantalum nitride (TaN) is 25% by mass, and Fe2LuO4The mass percentage content of (A) is 15%; the thickness of the first inorganic barrier layer is 120 nanometers;
(10) preparing a second organic barrier layer on the anode conductive substrate and covering the first inorganic barrier layer by vacuum evaporation with vacuum degree of 5 × 10-5Pa, evaporation rate ofThe material of the second organic barrier layer comprises 4,4',4' ' -tris (carbazol-9-yl) triphenylamine (TCTA) and bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum (Balq), wherein the molar ratio of TCTA to Balq is 50:100, and the thickness of the second organic barrier layer is 250 nm;
(11) preparing a second inorganic barrier layer by magnetron sputtering, wherein the second inorganic barrier layer is arranged on the anode conductive substrate and covered on the second organic barrier layer, and the background vacuum degree is 1 × 10-4Pa, the material of the second inorganic barrier layer comprises tantalum nitride (TaN) and iron lutetium (Fe)2LuO4) Wherein TaN occupies the second inorganic barrierThe mass percentage of the layer is 11%; the thickness of the second inorganic barrier layer is 120 nanometers; the first organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are sequentially covered on the light-emitting function layer and the cathode to form a packaging cover arranged on the anode conductive substrate;
(12) alternately repeating the steps (8) to (11) for 3 times to form 4 packaging covers which are sequentially covered on the luminous functional layer and the cathode, and packaging to obtain the structure of ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/TCTA:Balq/SnTe:TaN:Fe2LuO4/TCTA:Balq/TaN:Fe2LuO4The organic electroluminescent device of (1).
Example 6
The structure is ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/mCP:TAZ/PbTe:TiN:Y3Al5O12/mCP:TAZ/TiN:Y3Al5O12The encapsulation of the organic electroluminescent device of (1).
(1) Examples (7) to (7) are the same as example 1.
(8) Preparing a first organic barrier layer on the anode conductive substrate and covering the light-emitting functional layer and the cathode by vacuum evaporation with vacuum degree of 1 × 10-3Pa, evaporation rate ofThe material of the first organic barrier layer comprises 1, 3-bis (9H-carbazol-9-yl) benzene (mCP) and 3- (4-biphenyl) -4 phenyl-5-tert-butyl benzene-1, 2, 4-Triazole (TAZ), wherein the molar ratio of mCP to TAZ is 40:100, and the thickness of the first organic barrier layer is 250 nanometers;
(9) preparing a first inorganic barrier layer by magnetron sputtering, wherein the first inorganic barrier layer is arranged on the anode conductive substrate and covers the first organic barrier layer, and the background is trueThe degree of hollowness is 1 x 10-3Pa, the material of the first inorganic barrier layer comprises lead telluride (PbTe), titanium nitride (TiN) and yttrium aluminate (Y)3Al5O12) In the first inorganic barrier layer, titanium nitride (TiN) is 20% by mass, and Y is3Al5O12The mass percentage content of (A) is 20%; the thickness of the first inorganic barrier layer is 110 nanometers;
(10) preparing a second organic barrier layer on the anode conductive substrate and covering the first inorganic barrier layer by vacuum evaporation with vacuum degree of 1 × 10-3Pa, evaporation rate ofThe material of the second organic barrier layer comprises 1, 3-bis (9H-carbazol-9-yl) benzene (mCP) and 3- (4-biphenyl) -4 phenyl-5-tert-butyl benzene-1, 2, 4-Triazole (TAZ), wherein the molar ratio of mCP to TAZ is 40:100, and the thickness of the second organic barrier layer is 250 nm;
(11) preparing a second inorganic barrier layer by magnetron sputtering, wherein the second inorganic barrier layer is arranged on the anode conductive substrate and covered on the second organic barrier layer, and the background vacuum degree is 1 × 10-4Pa, the material of the second inorganic barrier layer comprises titanium nitride (TiN) and yttrium aluminate (Y)3Al5O12) Wherein, TiN accounts for 20 percent of the second inorganic barrier layer by mass; the thickness of the second inorganic barrier layer is 120 nanometers; the first organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are sequentially covered on the light-emitting function layer and the cathode to form a packaging cover arranged on the anode conductive substrate;
(12) alternately repeating the steps (8) to (11) for 2 times to form 3 packaging covers which are sequentially covered on the light-emitting functional layer and the cathode, and packaging to obtain a structure of ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3:Bphen/Al/mCP:TAZ/PbTe:TiN:Y3Al5O12/mCP:TAZ/TiN:Y3Al5O12The organic electroluminescent device of (1).
Comparative example 1
Has the structure of
ITO/MoO3:NPB/TCTA/Ir(ppy)3:TPBI/Bphen/CsN3Organic electroluminescent device package of Bphen/Al/mCP/PbTe/mCP/TiN
The encapsulation method was the same as in example 1. Different from example 1, the material of the first organic barrier layer was 1, 3-bis (9H-carbazol-9-yl) benzene (mCP), the material of the first inorganic barrier layer was lead telluride (PbTe), the material of the second organic barrier layer was 1, 3-bis (9H-carbazol-9-yl) benzene (mCP), and the material of the second inorganic barrier layer was titanium nitride (TiN), except that it was otherwise the same as example 1.
Table 1 shows the Water Vapor Transmission Rate (WVTR) and the service life of the organic electroluminescent devices of examples 1 to 6 and comparative example 1, and it can be seen from table 1 that the water vapor transmission rate of the organic electroluminescent devices of examples 1 to 6 is smaller than that of the organic electroluminescent device of comparative example 1, and the service life of the organic electroluminescent devices of comparative example 1 is longer than that of the organic electroluminescent device of comparative example 1.
TABLE 1 Water vapor Transmission Rate and service life of organic electroluminescent devices of examples 1 to 6 and comparative example 1
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. An organic electroluminescent device comprises an anode conductive substrate, a light-emitting functional layer, a cathode and a packaging cover, wherein the light-emitting functional layer and the cathode are sequentially stacked on the anode conductive substrate, and the packaging cover packages the light-emitting functional layer and the cathode on the anode conductive substrate; wherein,
the material of the first organic barrier layer includes a first hole transporting material which is N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-biphenyldiamine, N' -bis (α -naphthyl) -N, N '-diphenyl-4, 4' -diamine, 1-bis ((4-N, N '-bis (p-tolyl) amine) phenyl) cyclohexane, 2-methyl-9, 10-bis (imidazol-2-yl) anthracene, 4',4 "-tris (carbazol-9-yl) triphenylamine, or 1, 3-bis (9H-carbazol-9-yl) benzene, and a first electron transporting material which is 4, 7-diphenylphenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 8-hydroxyquinolinoaluminum, bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum, or 3- (4-biphenyl) -4-phenyl-5-tert-butyl-phenyl-1, 2, 4-triazole;
the material of the first inorganic barrier layer comprises telluride, first nitride and first alloy oxide, wherein the telluride is antimony telluride, bismuth telluride, cadmium telluride, indium telluride, tin telluride or lead telluride, the first nitride is silicon nitride, aluminum nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, and the first alloy oxide is magnesium metaaluminate, bismuth titanate, nickel chromate, cobalt chromate, iron lutetium or yttrium aluminate;
the material of the second organic barrier layer includes a second hole transporting material and a second electron transporting material, the second hole transporting material is N, N '-diphenyl-N, N' -bis (3-methylphenyl) -4,4 '-biphenyldiamine, N' -bis (α -naphthyl) -N, N '-diphenyl-4, 4' -diamine, 1-bis ((4-N, N '-bis (p-tolyl) amine) phenyl) cyclohexane, 2-methyl-9, 10-bis (imidazol-2-yl) anthracene, 4',4 ″ -tris (carbazol-9-yl) triphenylamine, or 1, 3-bis (9H-carbazol-9-yl) benzene, the second electron transporting material is 4, 7-diphenylphenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 8-hydroxyquinolinoaluminum, bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum or 3- (4-biphenyl) -4-phenyl-5-tert-butylbenzene-1, 2, 4-triazole;
the material of the second inorganic barrier layer comprises a second nitride and a second alloy oxide, the second nitride is silicon nitride, aluminum nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, and the second alloy oxide is magnesium metaaluminate, bismuth titanate, nickel chromate, cobalt chromate, iron lutetium or yttrium aluminate.
2. The organic electroluminescent device according to claim 1, wherein the number of the encapsulation covers is 3 to 5, and the 3 to 5 encapsulation covers are sequentially covered on the light-emitting functional layer and the cathode.
3. The organic electroluminescent device according to claim 1, wherein the molar ratio of the first hole transport material to the first electron transport material is 40:100 to 60: 100.
4. The organic electroluminescent device according to claim 1, wherein the first inorganic barrier layer contains 10 to 40 mass% of the first nitride and 10 to 30 mass% of the first alloy oxide.
5. The organic electroluminescent device according to claim 1, wherein the molar ratio of the second hole transport material to the second electron transport material is 40:100 to 60: 100.
6. The organic electroluminescent device according to claim 1, wherein the second nitride accounts for 10 to 40% by mass of the second inorganic barrier layer.
7. The organic electroluminescent device according to claim 1, wherein the first organic barrier layer and the second organic barrier layer have a thickness of 200 nm to 300 nm.
8. The organic electroluminescent device according to claim 1, wherein the first inorganic barrier layer and the second inorganic barrier layer have a thickness of 100 nm to 200 nm.
9. A packaging method of an organic electroluminescent device is characterized by comprising the following steps:
providing an anode conductive substrate, and forming a light-emitting functional layer on the anode conductive substrate through vacuum evaporation;
forming a cathode on the light-emitting functional layer by vacuum evaporation;
preparing a first organic barrier layer by vacuum evaporation, wherein the first organic barrier layer is arranged on the anode conductive substrate and covers the light-emitting functional layer and the cathode, the materials of the first organic barrier layer comprise a first hole transport material and a first electron transport material, the first hole transport material is N, N '-diphenyl-N, N' -di (3-methylphenyl) -4,4 '-biphenyldiamine, N' -di (alpha-naphthyl) -N, N '-diphenyl-4, 4' -diamine, 1-di ((4-N, N '-di (p-tolyl) amine) phenyl) cyclohexane, 2-methyl-9, 10-di (imidazol-2-yl) anthracene, 4',4'' -tri (carbazol-9-yl) triphenylamine or 1, 3-bis (9H-carbazol-9-yl) benzene, the first electron transport material being 4, 7-diphenylphenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 8-hydroxyquinoline aluminum, bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum, or 3- (4-biphenyl) -4 phenyl-5-tert-butyl-phenyl-1, 2, 4-triazole;
preparing a first inorganic barrier layer by magnetron sputtering, wherein the first inorganic barrier layer is arranged on the anode conductive substrate and covers the first organic barrier layer, the first inorganic barrier layer is made of telluride, a first nitride and a first alloy oxide, the telluride is antimony telluride, bismuth telluride, cadmium telluride, indium telluride, tin telluride or lead telluride, the first nitride is silicon nitride, aluminum nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, and the first alloy oxide is magnesium metaaluminate, bismuth titanate, nickel chromate, cobalt chromate, iron lutetium or yttrium aluminate;
preparing a second organic barrier layer by vacuum evaporation, wherein the second organic barrier layer is arranged on the anode conductive substrate and covers the first inorganic barrier layer, the material of the second organic barrier layer comprises a second hole transport material and a second electron transport material, the second hole transport material is N, N '-diphenyl-N, N' -di (3-methylphenyl) -4,4 '-biphenyldiamine, N' -di (alpha-naphthyl) -N, N '-diphenyl-4, 4' -diamine, 1-di ((4-N, N '-di (p-tolyl) amine) phenyl) cyclohexane, 2-methyl-9, 10-di (imidazol-2-yl) anthracene, 4',4'' -tri (carbazol-9-yl) triphenylamine or 1, 3-bis (9H-carbazol-9-yl) benzene, the second electron transport material being 4, 7-diphenylphenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 8-hydroxyquinoline aluminum, bis (2-methyl-8-quinoline) - (4-phenylphenol) aluminum, or 3- (4-biphenyl) -4 phenyl-5-tert-butyl-phenyl-1, 2, 4-triazole; and
preparing a second inorganic barrier layer by magnetron sputtering, wherein the second inorganic barrier layer is arranged on the anode conductive substrate and covers the second organic barrier layer, the first inorganic barrier layer, the second organic barrier layer and the second inorganic barrier layer are sequentially covered on the light-emitting function layer and the cathode to form a packaging cover arranged on the anode conductive substrate, and the packaging cover is packaged to obtain the organic electroluminescent device; the material of the second inorganic barrier layer comprises a second nitride and a second alloy oxide, wherein the second nitride is silicon nitride, aluminum nitride, boron nitride, hafnium nitride, tantalum nitride or titanium nitride, and the second alloy oxide is magnesium metaaluminate, bismuth titanate, nickel chromate, cobalt chromate, iron lutetium or yttrium aluminate.
10. The method for encapsulating an organic electroluminescent device according to claim 9,
in the step of preparing the first organic barrier layer by vacuum evaporation and the step of preparing the second organic barrier layer by vacuum evaporation, the vacuum degree of the vacuum evaporation is 1 × 10-5Pa～1×10-3Pa；
In the step of preparing the first inorganic barrier layer by magnetron sputtering and the step of preparing the second inorganic barrier layer by magnetron sputtering, the vacuum degree of the background is 1 multiplied by 10-5Pa～1×10-3Pa。
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