CN104078607A - Organic light-emitting diode device and manufacturing method thereof - Google Patents
Organic light-emitting diode device and manufacturing method thereof Download PDFInfo
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- CN104078607A CN104078607A CN201310109535.8A CN201310109535A CN104078607A CN 104078607 A CN104078607 A CN 104078607A CN 201310109535 A CN201310109535 A CN 201310109535A CN 104078607 A CN104078607 A CN 104078607A
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
An organic light-emitting diode device comprises an anode, a light-emitting layer, a cathode and a packaging cover, wherein the packaging cover packages the light-emitting layer and the cathode on the anode and comprises a first organic barrier layer, a first inorganic barrier layer formed on the surface of the first organic barrier layer, a second organic barrier layer formed on the surface of the first inorganic barrier layer and a second inorganic barrier layer formed on the second organic barrier layer. Materials of the first inorganic barrier layer include a nitride, a silicide and a carbide, and materials of the second inorganic barrier layer include a silicide and an oxide. The service life of the organic light-emitting diode device is long. The invention further provides a manufacturing method of the organic light-emitting diode device.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device and preparation method thereof.
Background technology
Organic electroluminescence device (OLED) is a kind of current mode light emitting semiconductor device based on organic material.Its typical structure is that the luminous organic material of preparing one deck tens nanometer thickness on ito glass is made luminescent layer, and there is the metal electrode of one deck low work function luminescent layer top.In the time being added with voltage on electrode, luminescent layer just produces light radiation.
Organic electroluminescence device is subject to after moisture and moisture erosion, can cause that the material of organic electroluminescence device inner member occurs aging and then lost efficacy, thereby the life-span of described organic electroluminescence device is shorter.
Summary of the invention
Based on this, be necessary to provide organic electroluminescence device that a kind of life-span grows and preparation method thereof.
A kind of organic electroluminescence device, comprise the anode, luminescent layer and the negative electrode that stack gradually, described organic electroluminescence device also comprises cap, described cap is packaged in described luminescent layer and negative electrode on described anode, and described cap comprises first organic barrier layer, be formed at the first inorganic barrier layer of described first organic barrier layer surface, be formed at second organic barrier layer on described the first inorganic barrier layer surface and be formed at the second inorganic barrier layer of described second organic barrier layer surface;
The material on described first organic barrier layer is selected from 1,1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described the first inorganic barrier layer comprises nitride, silicide and carbide, described nitride is selected from least one in aluminium nitride, titanium nitride, vanadium nitride, niobium nitride, zirconium nitride and tantalum nitride, described silicide is selected from least one in chromium silicide, tantalum silicide, hafnium suicide, titanium silicide, molybdenum silicide and tungsten silicide, and described carbide is selected from least one in aluminium carbide, chromium carbide, molybdenum carbide, niobium carbide, vanadium carbide and zirconium carbide;
The material on described second organic barrier layer is selected from 1,1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described the second inorganic barrier layer comprises silicide and oxide, described silicide is selected from least one in chromium silicide, tantalum silicide, hafnium suicide, titanium silicide, molybdenum silicide and tungsten silicide, and described oxide is selected from least one in magnesium oxide, alundum (Al2O3), titanium dioxide, zirconium dioxide, hafnium oxide and tantalum pentoxide.
In an embodiment, the quantity of described cap is that 2～4,2～4 caps stack gradually therein.
In an embodiment, the thickness on described first organic barrier layer is 200nm～300nm therein; The thickness of described the first inorganic barrier layer is 100nm～150nm; The thickness on described second organic barrier layer is 200nm～300nm; The thickness of described the second inorganic barrier layer is 100nm～150nm.
In an embodiment, described in described the first inorganic barrier layer, the quality percentage composition of silicide is 10%～30% therein, and the quality percentage composition of described carbide is 10%～30%.
In an embodiment, described in described the second inorganic barrier layer, the quality percentage composition of silicide is 10%～30% therein.
In an embodiment, described cap coordinates and is formed with host cavity with described anode therein, and described luminescent layer and negative electrode are all contained in described host cavity.
A preparation method for organic electroluminescence device, comprises the following steps:
Prepare luminescent layer at anode surface;
Prepare negative electrode on described luminescent layer surface; And
Prepare cap at described cathode surface, described cap is packaged in described luminescent layer and negative electrode on described anode, and described cap comprises first organic barrier layer, be formed at the first inorganic barrier layer of described first organic barrier layer surface, be formed at second organic barrier layer on described the first inorganic barrier layer surface and be formed at the second inorganic barrier layer of described second organic barrier layer surface, the material on described first organic barrier layer is selected from 1, 1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1, at least one in 10-Phen and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, the material of described the first inorganic barrier layer comprises nitride, silicide and carbide, described nitride is selected from aluminium nitride, titanium nitride, vanadium nitride, niobium nitride, at least one in zirconium nitride and tantalum nitride, described silicide is selected from chromium silicide, tantalum silicide, hafnium suicide, titanium silicide, at least one in molybdenum silicide and tungsten silicide, described carbide is selected from aluminium carbide, chromium carbide, molybdenum carbide, niobium carbide, at least one in vanadium carbide and zirconium carbide, the material on described second organic barrier layer is selected from 1,1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1, at least one in 10-Phen and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, the material of described the second inorganic barrier layer comprises silicide and oxide, described silicide is selected from chromium silicide, tantalum silicide, hafnium suicide, titanium silicide, at least one in molybdenum silicide and tungsten silicide, described oxide is selected from magnesium oxide, alundum (Al2O3), titanium dioxide, zirconium dioxide, at least one in hafnium oxide and tantalum pentoxide.
In an embodiment, the quantity of described cap is that 2～4,2～4 caps stack gradually therein.
In an embodiment, the thickness on described first organic barrier layer is 200nm～300nm therein; The thickness of described the first inorganic barrier layer is 100nm～150nm; The thickness on described second organic barrier layer is 200nm～300nm; The thickness of described the second inorganic barrier layer is 100nm～150nm.
In an embodiment, described cap coordinates and is formed with host cavity with described anode therein, and described luminescent layer and negative electrode are all contained in described host cavity.
Above-mentioned organic electroluminescence device and preparation method thereof, cap comprises the first organic barrier layer, the first inorganic barrier layer, second organic barrier layer, the second inorganic barrier layer that stack gradually, four layers of effectively corrosion of block water oxygen of cooperation, improve waterproof oxygen ability, thereby the life-span of organic electroluminescence device is longer.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device of an embodiment;
Fig. 2 is the preparation method's of the organic electroluminescent of an embodiment flow chart.
Embodiment
Below in conjunction with the drawings and specific embodiments, organic electroluminescence device and preparation method thereof is further illustrated.
Refer to Fig. 1, the organic electroluminescence device 100 of an execution mode comprises the anode with anode pattern 10, functional layer 20, negative electrode 30 and the cap 40 that stack gradually.
Anode 10 is electro-conductive glass or organic PETG (PET) film substrate that conducts electricity.On anode 10, there is the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm～150nm.
Functional layer 20 is formed at substrate 10 surfaces.Functional layer 20 comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the electron injecting layer that stack gradually.Be appreciated that hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer can omit, now functional layer 20 only comprises luminescent layer.
In present embodiment, the material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3).CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.
It should be noted that, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer also can adopt other materials as required.The thickness of hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer also can be adjusted as required.
Negative electrode 30 is formed at functional layer 20 surfaces.The thickness of negative electrode is 100nm.The material of negative electrode 30 is aluminium (Al).
Cap 40 is formed at the surface of negative electrode 30.In present embodiment, cap 40 covers at functional layer 20 and negative electrode 30, and the edge of cap 40 and anode 10 affixed, thereby functional layer 20 and negative electrode 30 are encapsulated on anode 10.Cap 40 is formed with host cavity.Host cavity is the groove from the surface of cap 40 depression.Functional layer 20 and negative electrode 30 are contained in host cavity by cap 40.
Cap 40 comprises the first organic barrier layer 41, the first inorganic barrier layer 42, second organic barrier layer 43 and the second inorganic barrier layer 44 that stack gradually.
First organic barrier layer 41 is formed at the surface of negative electrode 30, and the end face of covered cathode 30 and functional layer 20 and the part surface of anode 10, thereby just functional layer 20 and negative electrode 30 are encapsulated on anode 10.
The material on first organic barrier layer 41 is selected from 1,1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 4,7-diphenyl-1,10-Phen (BCP) and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).The thickness on first organic barrier layer 41 is 200nm～300nm.
The first inorganic barrier layer 42 is formed at the surface of the first inorganic barrier layer 41.The material of the first inorganic barrier layer 42 comprises nitride, silicide and carbide.Nitride is selected from least one in aluminium nitride (AlN), titanium nitride (TiN), vanadium nitride (VN), niobium nitride (NbN), zirconium nitride (ZrN) and tantalum nitride (TaN).Silicide is selected from chromium silicide (CrSi
2), tantalum silicide (TaSi
2), hafnium suicide (HfSi
2), titanium silicide (TiSi
2), molybdenum silicide (MoSi
2) and tungsten silicide (WSi
2) at least one.Carbide is selected from aluminium carbide (Al
4c
3), chromium carbide (Cr
3c
2), molybdenum carbide (Mo
2c), at least one in niobium carbide (NbC), vanadium carbide (VC) and zirconium carbide (ZrC).The thickness of the first inorganic barrier layer 42 is 100nm～150nm.
Further, in the first inorganic barrier layer 42, the quality percentage composition of silicide is 10%～30%, and the quality percentage composition of carbide is 10%～30%.
Second organic barrier layer 43 is formed at the surface of the first inorganic barrier layer 42.The material on second organic barrier layer 43 is selected from 1,1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 4,7-diphenyl-1,10-Phen (BCP) and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).The thickness on second organic barrier layer 43 is 200nm～300nm.
The second inorganic barrier layer 44 is formed at the surface on second organic barrier layer 43.The material of the second inorganic barrier layer 44 comprises silicide and oxide.Silicide is selected from chromium silicide (CrSi
2), tantalum silicide (TaSi
2), hafnium suicide (HfSi
2), titanium silicide (TiSi
2), molybdenum silicide (MoSi
2) and tungsten silicide (WSi
2) at least one.Oxide is selected from magnesium oxide (MgO), alundum (Al2O3) (Al
2o
3), titanium dioxide (TiO
2), zirconium dioxide (ZrO
2), hafnium oxide (HfO
2) and tantalum pentoxide (Ta
2o
5) at least one.The thickness of the second inorganic barrier layer 44 is 100nm～150nm.
Further, in the second inorganic barrier layer 44, the quality percentage composition of silicide is 10%～30%.
Preferably, the quantity of cap 40 is that 2～4,2～4 caps 40 stack gradually.2～4 caps 40 all cover at functional layer 20 and negative electrode 30, and the cap 40 that is positioned at outside covers on the cap 40 that is positioned at inner side, thereby multiple cap 40 forms following stepped construction: the first organic barrier layer 41/ first organic barrier layer of the inorganic barrier layer 42/ second 43/ second organic barrier layer of the inorganic barrier layer 44/.../the first 41/ first organic barrier layer of inorganic barrier layer 42/ second 43/ second inorganic barrier layer 44.
In above-mentioned organic electroluminescence device 100, cap 40 comprises the first organic barrier layer 41, the first inorganic barrier layer 42, second organic barrier layer 43 and the second inorganic barrier layer 44 that stack gradually, four layers of effectively corrosion of block water oxygen of cooperation, cap 40 is encapsulated in functional layer 20 and negative electrode 30 on anode 10, can effectively improve waterproof oxygen ability, thereby the life-span of organic electroluminescence device 100 is longer.
The host cavity that is appreciated that cap 40 can omit, and now directly on anode 10, host cavity is set.
Please refer to Fig. 2, the preparation method of the organic electroluminescence device 100 of an execution mode, it comprises the following steps:
Step S110, on anode 10, form functional layer 20.
Functional layer 20 comprises the hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, the electron injecting layer that stack gradually.
Anode 10 can be electro-conductive glass substrate or organic PETG (PET) film substrate that conducts electricity.Anode 10 has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm～150nm.
Preliminary treatment was first carried out to remove the pollutant on substrate 10 surfaces in anode 10 surfaces before forming functional layer 20, and the oxygen content of carrying out surface active increase anode 10 surfaces is to improve the work function on anode 10 surfaces.Be specially, anode 10 is adopted successively and removes the each Ultrasonic Cleaning 5min of acetone, ethanol, ionized water and ethanol, dry up afterwards with nitrogen, baking box is dried.
In present embodiment, the material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
It should be noted that, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer also can adopt other materials as required.Hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer can omit, and now functional layer 20 only comprises luminescent layer.
Step S120, form negative electrodes 30 on functional layer 20 surface.
The material of negative electrode 30 is aluminium (Al).The thickness of negative electrode 30 is 100nm.Negative electrode 30 is formed by vacuum evaporation, and vacuum degree is 5 × 10
-5pa, evaporation rate is
Step S130, prepare cap 40 on negative electrode 30 surfaces.
Cap 40 is formed at the surface of negative electrode 30.In present embodiment, cap 40 covers at functional layer 20 and negative electrode 30, and the edge of cap 40 and anode 10 affixed, thereby functional layer 20 and negative electrode 30 are encapsulated on anode 10.Cap 40 is formed with host cavity.Host cavity is the groove from the surface of cap 40 depression.Functional layer 20 and negative electrode 30 are contained in host cavity by cap 40.
Cap 40 comprises the first organic barrier layer 41, the first inorganic barrier layer 42, second organic barrier layer 43 and the second inorganic barrier layer 44 that stack gradually.
First organic barrier layer 41 is formed at the surface of negative electrode 30, and the end face of covered cathode 30 and functional layer 20 and the part surface of anode 10, thereby just functional layer 20 and negative electrode 30 are encapsulated on anode 10.
The material on first organic barrier layer 41 is selected from 1,1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 4,7-diphenyl-1,10-Phen (BCP) and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).The thickness on first organic barrier layer 41 is 200nm～300nm.
First organic barrier layer 41 is formed by vacuum evaporation, and vacuum degree is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate
The first inorganic barrier layer 42 is formed at the surface of the first inorganic barrier layer 41.The material of the first inorganic barrier layer 42 comprises nitride, silicide and carbide.Nitride is selected from least one in aluminium nitride (AlN), titanium nitride (TiN), vanadium nitride (VN), niobium nitride (NbN), zirconium nitride (ZrN) and tantalum nitride (TaN).Silicide is selected from chromium silicide (CrSi
2), tantalum silicide (TaSi
2), hafnium suicide (HfSi
2), titanium silicide (TiSi
2), molybdenum silicide (MoSi
2) and tungsten silicide (WSi
2) at least one.Carbide is selected from aluminium carbide (Al
4c
3), chromium carbide (Cr
3c
2), molybdenum carbide (Mo
2c), at least one in niobium carbide (NbC), vanadium carbide (VC) and zirconium carbide (ZrC).The thickness of the first inorganic barrier layer 42 is 100nm～150nm.
The first inorganic barrier layer 42 is prepared by magnetron sputtering, and base vacuum degree is 1 × 10
-5pa～1 × 10
-3pa.
Further, in the first inorganic barrier layer 42, the quality percentage composition of silicide is 10%～30%, and the quality percentage composition of carbide is 10%～30%.
Second organic barrier layer 43 is formed at the surface of the first inorganic barrier layer 42.The material on second organic barrier layer 43 is selected from 1,1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine (m-MTDATA), 4,7-diphenyl-1,10-Phen (BCP) and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi).The thickness on second organic barrier layer 43 is 200nm～300nm.
Second organic barrier layer 43 is formed by vacuum evaporation, and vacuum degree is 1 × 10
-5pa～1 × 10
-3pa, evaporation rate
The second inorganic barrier layer 44 is formed at the surface on second organic barrier layer 43.The material of the second inorganic barrier layer 44 comprises silicide and oxide.Silicide is selected from chromium silicide (CrSi
2), tantalum silicide (TaSi
2), hafnium suicide (HfSi
2), titanium silicide (TiSi
2), molybdenum silicide (MoSi
2) and tungsten silicide (WSi
2) at least one.Oxide is selected from magnesium oxide (MgO), alundum (Al2O3) (Al
2o
3), titanium dioxide (TiO
2), zirconium dioxide (ZrO
2), hafnium oxide (HfO
2) and tantalum pentoxide (Ta
2o
5) at least one.The thickness of the second inorganic barrier layer 44 is 100nm～150nm.
The second inorganic barrier layer 44 is prepared by magnetron sputtering, and base vacuum degree is 1 × 10
-5pa～1 × 10
-3pa.
Further, in the second inorganic barrier layer 44, the quality percentage composition of silicide is 10%～30%.
Preferably, the quantity of cap 40 is that 2～4,2～4 caps 40 stack gradually.2～4 caps 40 all cover at functional layer 20 and negative electrode 30, and the cap 40 that is positioned at outside covers on the cap 40 that is positioned at inner side, thereby multiple cap 40 forms following stepped construction: the first organic barrier layer 41/ first organic barrier layer of the inorganic barrier layer 42/ second 43/ second organic barrier layer of the inorganic barrier layer 44/.../the first 41/ first organic barrier layer of inorganic barrier layer 42/ second 43/ second inorganic barrier layer 44.
Cap 40 is formed at the surface of negative electrode 30.In present embodiment, cap 40 covers at functional layer 20 and negative electrode 30, and the edge of cap 40 and anode 10 affixed, thereby functional layer 20 and negative electrode 30 are encapsulated on anode 10.Cap 40 is formed with host cavity.Host cavity is the groove from the surface of cap 40 depression.Functional layer 20 and negative electrode 30 are contained in host cavity by cap 40.
The host cavity that is appreciated that cap 40 can omit, and now directly on anode 10, host cavity is set.
The preparation method of above-mentioned organic electroluminescence device, preparation technology is simple, easily preparation in enormous quantities.
Below in conjunction with specific embodiment, organic electroluminescence device preparation method provided by the invention is elaborated.
Embodiment 1
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap; Wherein, brace "/" represents layer structure, and colon ": " represents doping, lower same.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode is electro-conductive glass.Anode has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Anode surface first carried out preliminary treatment to remove the pollutant on substrate 10 surfaces before forming functional layer, and the oxygen content of carrying out surface active increase anode surface is to improve the work function of anode surface.Be specially, anode is adopted to the each Ultrasonic Cleaning 5min of acetone, ethanol, ionized water and ethanol successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
2, form negative electrode on functional layer surface.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
3, prepare cap at cathode surface.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises the first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer that stack gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material is TAPC, vacuum degree 1 × 10
-5pa, evaporation rate
thickness 300nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises WSi
2, AlN and Al
4c
3, base vacuum degree 1 × 10
-5pa, WSi
2quality percentage composition be 20%, Al
4c
3quality percentage composition be 16%, all the other are AlN, thickness 150nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material is TAPC, vacuum degree 1 × 10
-5pa, evaporation rate
thickness 300nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises CrSi
2and MgO, base vacuum degree 1 × 10
-5pa, CrSi
2quality percentage composition be 30%, all the other are MgO, thickness 150nm;
The quantity of cap is that 4,4 caps stack gradually.The structure of cap is (TAPC/WSi
2: AlN:Al
4c
3/ TAPC/CrSi
2: MgO)
4
Embodiment 2
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode is electro-conductive glass.Anode has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Anode surface first carried out preliminary treatment to remove the pollutant on substrate 10 surfaces before forming functional layer, and the oxygen content of carrying out surface active increase anode surface is to improve the work function of anode surface.Be specially, anode is adopted to the each Ultrasonic Cleaning 5min of acetone, ethanol, ionized water and ethanol successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
2, form negative electrode on functional layer surface.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
3, at cathode surface evaporation protective layer.
The material of protective layer is NPB.The thickness of protective layer 40 is 300nm.Protective layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
4, prepare cap at protective layer.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises the first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer that stack gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material is NPB, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 250nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises MoSi
2, TiN and Cr
3c
2, adopt base vacuum degree 1 × 10
-5pa, MoSi
2quality percentage composition be 30%, Cr
3c
2quality percentage composition be 10%, all the other are TiN, thickness 150nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material is NPB, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 250nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises TaSi
2and Al
2o
3, base vacuum degree 1 × 10
-4pa, TaSi
2quality percentage composition be 10%, all the other are Al
2o
3, thickness 130nm;
The quantity of cap is that 3,3 caps stack gradually.The structure of cap is (NPB/MoSi
2: TiN:Cr
3c
2/ NPB/TaSi
2: Al
2o
3)
3
Embodiment 3
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode is electro-conductive glass.Anode has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Anode surface first carried out preliminary treatment to remove the pollutant on substrate 10 surfaces before forming functional layer, and the oxygen content of carrying out surface active increase anode surface is to improve the work function of anode surface.Be specially, anode is adopted to the each Ultrasonic Cleaning 5min of acetone, ethanol, ionized water and ethanol successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
2, form negative electrode on functional layer surface.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
3, prepare cap at cathode surface.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises the first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer that stack gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material is Alq3, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 200nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises TiSi
2, VN and Mo
2c, base vacuum degree 5 × 10
-5pa, TiSi
2quality percentage composition be 10%, Mo
2the quality percentage composition of C is 30%, and all the other are VN, thickness 100nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material is Alq3, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 200nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises HfSi
2and TiO
2, base vacuum degree 1 × 10
-4pa, HfSi
2quality percentage composition be 20%, all the other are TiO
2, thickness 100nm;
The quantity of cap is that 3,3 caps stack gradually.The structure of cap is (Alq3/TiSi
2: VN:Mo
2c/Alq3/HfSi
2: TiO
2)
3
Embodiment 4
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode is electro-conductive glass.Anode has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 150nm.
Anode surface first carried out preliminary treatment to remove the pollutant on substrate 10 surfaces before forming functional layer, and the oxygen content of carrying out surface active increase anode surface is to improve the work function of anode surface.Be specially, anode is adopted to the each Ultrasonic Cleaning 5min of acetone, ethanol, ionized water and ethanol successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
2, form negative electrode on functional layer surface.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
3, at cathode surface evaporation protective layer.
The material of protective layer is SiO.The thickness of protective layer 40 is 200nm.Protective layer is formed by vacuum evaporation, and vacuum degree is 5 × 10
-5pa, evaporation rate is
4, prepare cap at protective layer.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises the first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer that stack gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material is m-MTDATA, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 250nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises HfSi
2, NbN and NbC, adopt base vacuum degree 5 × 10
-5pa, HfSi
2quality percentage composition be 20%, NbC quality percentage composition is 15%, all the other are NbN, thickness 120nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material is m-MTDATA, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 250nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises TiSi
2and ZrO
2, base vacuum degree 1 × 10
-4pa, TiSi
2quality percentage composition be 15%, all the other are ZrO
2, thickness 110nm;
The quantity of cap is that 3,3 caps stack gradually.The structure of cap is (m-MTDATA/HfSi
2: NbN:NbC/m-MTDATA/TiSi
2: ZrO
2)
3
Embodiment 5
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode is electro-conductive glass.Anode has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 120nm.
Anode surface first carried out preliminary treatment to remove the pollutant on substrate 10 surfaces before forming functional layer, and the oxygen content of carrying out surface active increase anode surface is to improve the work function of anode surface.Be specially, anode is adopted to the each Ultrasonic Cleaning 5min of acetone, ethanol, ionized water and ethanol successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
2, form negative electrode on functional layer surface.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 5 × 10
-5pa, evaporation rate is
3, prepare cap at cathode surface.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises the first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer that stack gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material is BCP, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 250nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises TaSi
2, ZrN and VC, base vacuum degree 5 × 10
-5pa, TaSi
2quality percentage composition be 15%, VC quality percentage composition is 10%, all the other are ZrN, thickness 130nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material is BCP, vacuum degree 5 × 10
-5pa, evaporation rate
thickness 250nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises MoSi
2and HfO
2, base vacuum degree 1 × 10
-4pa, MoSi
2content is 17%, and all the other are HfO
2, thickness 110nm;
The quantity of cap is that 3,3 caps stack gradually.The structure of cap is (BCP/TaSi
2: ZrN:VC/BCP/MoSi
2: HfO
2)
3
Embodiment 6
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode is electro-conductive glass.Anode has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Anode surface first carried out preliminary treatment to remove the pollutant on substrate 10 surfaces before forming functional layer, and the oxygen content of carrying out surface active increase anode surface is to improve the work function of anode surface.Be specially, anode is adopted to the each Ultrasonic Cleaning 5min of acetone, ethanol, ionized water and ethanol successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
2, form negative electrode on functional layer surface.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
3, prepare cap at cathode surface.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises the first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer that stack gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material is TPBi, vacuum degree 1 × 10
-3pa, evaporation rate
thickness 250nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises CrSi
2, TaN and ZrC, base vacuum degree 1 × 10
-3pa, CrSi
2quality percentage composition be 15%, ZrC quality percentage composition is 30%, all the other are TaN, thickness 120nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material is TPBi, vacuum degree 1 × 10
-3pa, evaporation rate
thickness 250nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material comprises WSi
2and Ta
2o
5, base vacuum degree 1 × 10
-3pa, WSi
2content is 20%, and all the other are Ta
2o
5, thickness 100nm;
The quantity of cap is that 2,2 caps stack gradually.The structure that 2 caps stack gradually is (TPBi/CrSi
2: TaN:ZrC/TPBi/WSi
2: Ta
2o
5)
2
Comparative example
The present embodiment is prepared structure: ITO/NPB:MoO
3/ TCTA/TPBI:Ir (ppy)
3/ Bphen/Bphen:CsN
3the organic electroluminescence device of/Al/ cap.
The preparation method of above-mentioned organic electroluminescence device, comprises the following steps:
1, on anode, form functional layer.
Anode is electro-conductive glass.Anode has the ITO layer of the anode pattern of being prepared with.The thickness of ITO layer is 100nm.
Anode surface first carried out preliminary treatment to remove the pollutant on substrate 10 surfaces before forming functional layer, and the oxygen content of carrying out surface active increase anode surface is to improve the work function of anode surface.Be specially, anode is adopted to the each Ultrasonic Cleaning 5min of acetone, ethanol, ionized water and ethanol successively, dry up afterwards with nitrogen, baking box is dried.
The material of hole injection layer comprises N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4-4 '-diamines (NPB) and be entrained in the molybdenum oxide (MoO in NPB
3).MoO
3quality percentage composition be 30%.The thickness of hole injection layer is 10nm.Hole injection layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of hole transmission layer is 4,4', 4''-tri-(carbazole-9-yl) triphenylamine (TCTA).The thickness of hole transmission layer is 30nm.Hole transmission layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of luminescent layer comprises material of main part and is entrained in the guest materials in material of main part.Material of main part is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), and guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy)
3).The quality percentage composition of guest materials is 5%.The thickness of luminescent layer is 20nm.Luminescent layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron transfer layer is 4,7-diphenyl-1,10-phenanthroline (Bphen).The thickness of electron transfer layer is 10nm.Electron transfer layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
The material of electron injecting layer comprises Bphen and is entrained in the nitrine caesium (CsN in Bphen
3), CsN
3quality percentage composition be 30%.The thickness of electron injecting layer is 20nm.Electron injecting layer is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
2, form negative electrode on functional layer surface.
The material of negative electrode is aluminium.The thickness of negative electrode is 100nm.Negative electrode is formed by vacuum evaporation, and vacuum degree is 3 × 10
-5pa, evaporation rate is
3, prepare cap at cathode surface.
Cap is formed at the surface of negative electrode, and the end face of covered cathode and functional layer and the part surface of anode, thereby just functional layer and negative electrode are encapsulated on anode.
Cap comprises the first organic barrier layer, the first inorganic barrier layer, second organic barrier layer and the second inorganic barrier layer that stack gradually.
First organic barrier layer adopts vacuum evaporation preparation, and material is TAPC, vacuum degree 1 × 10
-5pa, evaporation rate
thickness 300nm;
The first inorganic barrier layer is prepared by magnetron sputtering, and material comprises WSi
2, base vacuum degree 1 × 10
-5pa, thickness 150nm;
Second organic barrier layer adopts vacuum evaporation preparation, and material is TAPC, vacuum degree 1 × 10
-5pa, evaporation rate
thickness 300nm;
The second inorganic barrier layer is prepared by magnetron sputtering, and material is MgO, base vacuum degree 1 × 10
-5pa, thickness 150nm;
The quantity of cap is that 4,4 caps stack gradually.The structure of cap is (TAPC/WSi
2/ TAPC/MgO)
4
The preparation used of the embodiment of the present invention and comparative example and tester are: high vacuum coating equipment (scientific instrument development center, Shenyang Co., Ltd, pressure <1 × 10-3Pa), magnetron sputtering apparatus (scientific instrument development center, Shenyang Co., Ltd), current-voltage tester (Keithly company of the U.S., 2400), chroma-luminance meter (Konica Minolta, model: CS-100A) model:.
Refer to table 1, table 1 is depicted as the test result of the aqueous vapor penetrance (Water Vapor Transmission Rate) of organic electroluminescence device prepared by embodiment 1～embodiment 6 and comparative example.The aqueous vapor penetrance of the organic electroluminescence device that as can be seen from Table 1 prepared by embodiment 1～embodiment 6 is all less than 6.0 × 10
-4g/m
2/ day, the aqueous vapor penetrance (7.1 × 10 of the organic electroluminescence device of preparing much smaller than comparative example
-3g/m
2/ day) waterproof effect is better, can effectively reduce the erosion of outside aqueous vapor to organic electroluminescence device, thus improve the life-span of organic electroluminescence device.
Table 1
| ? | WVTR(g/m 2/day) |
| Embodiment 1 | 4.5×10 -4 |
| Embodiment 2 | 5.1×10 -4 |
| Embodiment 3 | 5.2×10 -4 |
| Embodiment 4 | 5.5×10 -4 |
| Embodiment 5 | 5.7×10 -4 |
| Embodiment 6 | 6.0×10 -4 |
| Comparative example | 7.1×10 -3 |
Refer to table 2, it is 1000cd/m at original intensity that table 2 is depicted as organic electroluminescence device prepared by embodiment 1～embodiment 6 and comparative example
2condition under life-span (brightness is reduced to original intensity 70% time used).
Table 2
The initial brightness of the organic electroluminescence device that as can be seen from Table 2, prepared by embodiment 1～embodiment 6 is 1000cd/m
2time, the life-span reaches more than 5785 hours, and the life-span is longer.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. an organic electroluminescence device, comprise the anode, luminescent layer and the negative electrode that stack gradually, it is characterized in that: described organic electroluminescence device also comprises cap, described cap is packaged in described luminescent layer and negative electrode on described anode, and described cap comprises first organic barrier layer, be formed at the first inorganic barrier layer of described first organic barrier layer surface, be formed at second organic barrier layer on described the first inorganic barrier layer surface and be formed at the second inorganic barrier layer of described second organic barrier layer surface;
The material on described first organic barrier layer is selected from 1,1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described the first inorganic barrier layer comprises nitride, silicide and carbide, described nitride is selected from least one in aluminium nitride, titanium nitride, vanadium nitride, niobium nitride, zirconium nitride and tantalum nitride, described silicide is selected from least one in chromium silicide, tantalum silicide, hafnium suicide, titanium silicide, molybdenum silicide and tungsten silicide, and described carbide is selected from least one in aluminium carbide, chromium carbide, molybdenum carbide, niobium carbide, vanadium carbide and zirconium carbide;
The material on described second organic barrier layer is selected from 1,1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1,10-Phen and 1, at least one in 3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene;
The material of described the second inorganic barrier layer comprises silicide and oxide, described silicide is selected from least one in chromium silicide, tantalum silicide, hafnium suicide, titanium silicide, molybdenum silicide and tungsten silicide, and described oxide is selected from least one in magnesium oxide, alundum (Al2O3), titanium dioxide, zirconium dioxide, hafnium oxide and tantalum pentoxide.
2. organic electroluminescence device according to claim 1, is characterized in that, the quantity of described cap is that 2～4,2～4 caps stack gradually.
3. organic electroluminescence device according to claim 1, is characterized in that, the thickness on described first organic barrier layer is 200nm～300nm; The thickness of described the first inorganic barrier layer is 100nm～150nm; The thickness on described second organic barrier layer is 200nm～300nm; The thickness of described the second inorganic barrier layer is 100nm～150nm.
4. organic electroluminescence device according to claim 1, is characterized in that, described in described the first inorganic barrier layer, the quality percentage composition of silicide is 10%～30%, and the quality percentage composition of described carbide is 10%～30%.
5. organic electroluminescence device according to claim 1, is characterized in that, described in described the second inorganic barrier layer, the quality percentage composition of silicide is 10%～30%.
6. organic electroluminescence device according to claim 1, is characterized in that, described cap coordinates and is formed with host cavity with described anode, and described luminescent layer and negative electrode are all contained in described host cavity.
7. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
Prepare luminescent layer at anode surface;
Prepare negative electrode on described luminescent layer surface; And
Prepare cap at described cathode surface, described cap is packaged in described luminescent layer and negative electrode on described anode, and described cap comprises first organic barrier layer, be formed at the first inorganic barrier layer of described first organic barrier layer surface, be formed at second organic barrier layer on described the first inorganic barrier layer surface and be formed at the second inorganic barrier layer of described second organic barrier layer surface, the material on described first organic barrier layer is selected from 1, 1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1, at least one in 10-Phen and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, the material of described the first inorganic barrier layer comprises nitride, silicide and carbide, described nitride is selected from aluminium nitride, titanium nitride, vanadium nitride, niobium nitride, at least one in zirconium nitride and tantalum nitride, described silicide is selected from chromium silicide, tantalum silicide, hafnium suicide, titanium silicide, at least one in molybdenum silicide and tungsten silicide, described carbide is selected from aluminium carbide, chromium carbide, molybdenum carbide, niobium carbide, at least one in vanadium carbide and zirconium carbide, the material on described second organic barrier layer is selected from 1,1-bis-((4-N, N '-bis-(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-aminomethyl phenyl-N-phenyl amino) triphenylamine, 4,7-diphenyl-1, at least one in 10-Phen and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene, the material of described the second inorganic barrier layer comprises silicide and oxide, described silicide is selected from chromium silicide, tantalum silicide, hafnium suicide, titanium silicide, at least one in molybdenum silicide and tungsten silicide, described oxide is selected from magnesium oxide, alundum (Al2O3), titanium dioxide, zirconium dioxide, at least one in hafnium oxide and tantalum pentoxide.
8. the preparation method of organic electroluminescence device according to claim 7, is characterized in that, the quantity of described cap is that 2～4,2～4 caps stack gradually.
9. the preparation method of organic electroluminescence device according to claim 7, is characterized in that: the thickness on described first organic barrier layer is 200nm～300nm; The thickness of described the first inorganic barrier layer is 100nm～150nm; The thickness on described second organic barrier layer is 200nm～300nm; The thickness of described the second inorganic barrier layer is 100nm～150nm.
10. the preparation method of organic electroluminescence device according to claim 7, is characterized in that: described cap coordinates and is formed with host cavity with described anode, and described luminescent layer and negative electrode are all contained in described host cavity.
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