CN103855323A - Organic light-emitting device and preparation method thereof - Google Patents
Organic light-emitting device and preparation method thereof Download PDFInfo
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- CN103855323A CN103855323A CN201210501398.8A CN201210501398A CN103855323A CN 103855323 A CN103855323 A CN 103855323A CN 201210501398 A CN201210501398 A CN 201210501398A CN 103855323 A CN103855323 A CN 103855323A
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- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- 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
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- 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
Abstract
Provided in the invention is an organic light-emitting device comprising an anode conductive substrate, a functional layer, a light-emitting layer, a cathode layer and a packaging layer. The anode conductive substrate, the functional layer, the light-emitting layer, the cathode layer and the packaging layer are successively laminated; the anode conductive substrate and the packaging layer form an enclosed space; and the functional layer, the light-emitting layer, and the cathode layer are accommodated into the enclosed space. The packaging layer successively includes a protection layer, a blocking layer, and an aluminum-contained polyethylene terephthalate film; and the blocking layer successively includes a first sulfide layer, a second sulfide layer, and an organic blocking layer. In addition, the invention also provides a preparation method of the organic light-emitting device. With the method, erosion on the organic light-emitting device by moisture and oxygen can be effectively reduced, so that the service life of the organic light-emitting device can be obviously prolonged. The method is especially suitable for packaging of a flexible organic light-emitting device.
Description
Technical field
The present invention relates to electronic device association area, relate in particular 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 tens nanometer thickness on ito glass is made luminescent layer, and there is the metal electrode of low work function luminescent layer top.In the time being added with voltage on electrode, luminescent layer just produces light radiation.
OLED device have active illuminating, luminous efficiency high, low in energy consumption, light, thin, without advantages such as angle limitations, thought to be most likely at by insider the device of new generation that occupies dominance on following illumination and display device market.As a brand-new illumination and Display Technique, the ten years development in the past of OLED technology is swift and violent, has obtained huge achievement.Throw light on because the whole world is increasing and show that producer drops into research and development one after another, having promoted greatly the industrialization process of OLED, making the growth rate of OLED industry surprising, having arrived the eve of scale of mass production at present.
Flexible product is the development trend of organic electroluminescence device, but the current ubiquity life-span is short, and therefore the quality of encapsulation directly affects the life-span of device.In conventional art, adopt glass cover or crown cap to encapsulate, ultraviolet polymerization resin sealing for its edge, but the glass cover using in this method or crown cap volume are often larger, increased the weight of device, and the method can not be applied to the give out light encapsulation of device of flexible organic electroluminescence.
Summary of the invention
For overcoming the defect of above-mentioned prior art, the invention provides a kind of organic electroluminescence device and preparation method thereof.This organic electroluminescence device can reduce steam, the erosion of oxygen to organic electroluminescence device effectively, and organic functional material and the electrode of protection organic electroluminescence device exempt from destruction, and the life-span of flexible OLED device is increased significantly.The inventive method is applicable to the organic electroluminescence device prepared with conducting glass substrate of encapsulation, is also applicable to the flexible organic electroluminescent device that encapsulation is prepared as substrate take plastics or metal.The inventive method is particularly useful for encapsulating flexible organic electroluminescent device.
On the one hand, the invention provides a kind of organic electroluminescence device, comprise the anode conducting substrate, functional layer, luminescent layer, cathode layer and the encapsulated layer that stack gradually, anode conducting substrate and encapsulated layer form enclosure space, functional layer, luminescent layer and cathode layer are contained in this enclosure space, and described encapsulated layer comprises successively protective layer, barrier layer and contains aluminium polyethylene terephthalate film;
Described barrier layer comprises the first sulfurized layer, the second sulfurized layer and organic barrier layer successively;
Described the first sulfurized layer is identical with the second sulfurized layer material, is tungsten disulfide (WS
2), molybdenum bisuphide (MoS
2), tantalum disulfide (TaS
2), curing niobium (NbS
2), antimonous sulfide (Sb
2s
3) or orpiment (As
2s
3);
The material on described organic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin.
Sulfurized layer compactness is high, and waterproof oxygen ability is strong, can reduce the destruction that moisture produces device.
Adopt different preparation methods to prepare two-layer identical sulfurized layer, can improve barrier properties, effectively release slow organic electroluminescence device stress in thin film, prevent the bending and damaged of device.
Preferably, the thickness of described the first sulfurized layer is 100～150nm.
Preferably, the thickness of described the second sulfurized layer is 100～150nm.
The existence on organic barrier layer can stop outside water, the erosion of oxygen isoreactivity material to organic electroluminescence device on the one hand, can increase on the other hand the flexibility of encapsulated layer, prevent the appearance crackle of encapsulated layer, simultaneously organic barrier layer have quality light, prepare the advantages such as easy.The pliability of encapsulated layer has been strengthened in the preparation that repeats on organic barrier layer.
Preferably, the thickness on described organic barrier layer is 1～1.5 μ m.
Preferably, described the first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, and described barrier layer is that 4～7 basic structures repeat to form.
The first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, described barrier layer is that multiple basic structure repeats to form, water, oxygen permeation pathway are extended, can reach good packaging effect, effectively reduce outside water, the erosion of oxygen isoreactivity material to organic electroluminescence device, make up the shortcoming on single sulfurized layer and single organic substance barrier layer, extended device lifetime.
The existence of protective layer can protect negative electrode to exempt from destruction in subsequent operation process.
Preferably; described protective layer material is selected from the one in organic small molecule material, inorganic material or metal material, preferably from CuPc (CuPc), N, and N '-(1-naphthyl)-N; N '-diphenyl-4,4 '-benzidine (NPB), 8-hydroxyquinoline aluminum (Alq
3), silica (SiO), magnesium fluoride (MgF
2) or zinc sulphide (ZnS).Preferably, the thickness of protective layer is 200～300nm.
Preferably, described anode conducting substrate is conducting glass substrate or conduction organic film substrate.
More preferably, described anode conducting substrate is tin indium oxide (ITO) conducting glass substrate.
Functional layer generally includes hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer.Luminescent layer is arranged between hole transmission layer and electron transfer layer.Preferably, functional layer and luminescent layer are the method setting by vacuum evaporation.
Preferably, cathode layer can be non-transparent metals negative electrode (aluminium, silver, gold etc.) layer or transparent cathode layer (dielectric layer/metal level/dielectric layer etc., as ITO/Ag/ITO, ZnS/Ag/ZnS etc.).
More preferably, described cathode layer is aluminium.
Containing aluminium polyethylene terephthalate film (PET) edge-coating epoxy encapsulation glue, by the dry sclerosis of the mode packaging plastic of ultraviolet curing, described organic electroluminescence device is encapsulated in described containing in aluminium polyethylene terephthalate film and substrate.
On the other hand, the invention provides a kind of preparation method of organic electroluminescence device, comprise the following steps:
(1) on clean conducting glass substrate or conduction organic film substrate, be prepared with the anode pattern of organic electroluminescence devices; Adopt the method for vacuum evaporation on anode conducting substrate, to prepare successively functional layer, luminescent layer, cathode layer and protective layer;
(2) preparation method on barrier layer is as follows:
(a) adopt the method for reaction magnetocontrol sputtering on protective layer, to prepare the first sulfurized layer, the material of described the first sulfurized layer is WS
2, MoS
2, TaS
2, NbS
2, Sb
2s
3or As
2s
3;
(b) adopt the method for non-reaction magnetocontrol sputtering on protective layer, to prepare the second sulfurized layer, the material of described the second sulfurized layer is WS
2, MoS
2, TaS
2, NbS
2, Sb
2s
3or As
2s
3;
(c) adopt the method for first spin coating post-exposure on sulfurized layer, to prepare organic barrier layer, the material on described organic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin;
(3), containing aluminium polyethylene terephthalate film edge-coating epoxy encapsulation glue, by the dry sclerosis of the mode packaging plastic of ultraviolet curing, described organic electroluminescence device is encapsulated in described containing in aluminium polyethylene terephthalate film and substrate.
Sulfurized layer compactness is high, and waterproof oxygen ability is strong, can reduce the destruction that moisture produces device.
The two-layer identical sulfurized layer that adopts different preparation methods to prepare, can improve barrier properties, effectively releases slow organic electroluminescence device stress in thin film.
Preferably, while adopting reaction magnetocontrol sputtering to prepare described the first sulfurized layer, sputtering target material is W, Mo, Ta, Nb, Sb or As, pass into the mist that gas is hydrogen sulfide and argon gas, the volume fraction that described hydrogen sulfide accounts for mist is 3% ~ 17%, gas flow is 10～15sccm, and when sputter, base vacuum degree is 1 × 10
-5～1 × 10
-3pa, preferably, the first sulfurized layer thickness is 100～150nm.
Preferably, while adopting non-reaction magnetocontrol sputtering to prepare described the second sulfurized layer, sputtering target material is WS
2, MoS
2, TaS
2, NbS
2, Sb
2s
3or As
2s
3, passing into gas is argon gas, and gas flow is 10～15sccm, and when sputter, base vacuum degree is 1 × 10
-5～1 × 10
-3pa, preferably, the second sulfurized layer thickness is 100～150nm.
While preparing sulfurized layer by reactive sputtering; exist in the situation of reacting gas hydrogen sulfide, target can react with reacting gas and form sulfide, and the thin film composition that reactive sputtering generates is pure; film thickness even compact; surface topography is good, strong with protective layer adhesion, is conducive to the sputter of the second sulfurized layer at the first sulfurized layer; the existence of the first sulfurized layer and the second sulfurized layer; reduce to a certain extent stress in thin film, avoided the appearance of the defect such as space, crack, improved barrier properties.
The existence on organic barrier layer can stop outside water, the erosion of oxygen isoreactivity material to organic electroluminescence device on the one hand, can increase on the other hand the flexibility of encapsulated layer, prevent the appearance crackle of encapsulated layer, simultaneously organic barrier layer have quality light, prepare the advantages such as easy.The pliability of encapsulated layer has been strengthened in the preparation that repeats on organic barrier layer.
Preferably, while adopting the method for first spin coating post-exposure to prepare organic barrier layer, preparation condition is: under inert atmosphere, behind the organic barrier layer of spin coating, be cured with UV light (λ=365nm), light intensity is 10～15mW/cm
2, the time for exposure is 150～200s.
Preferably, after step (c), adopt method and the material identical with step (a) on organic barrier layer, to prepare the first sulfurized layer, on described the first sulfurized layer, adopt again method and the material that step (b) is identical to prepare the second sulfurized layer, on the second described sulfurized layer, adopt method and the material identical with step (c) to prepare organic barrier layer, described the first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, prepare multiple described basic structure and repeat to form barrier layer.
The first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, described barrier layer is that multiple basic structure repeats to form, water, oxygen permeation pathway are extended, can reach good packaging effect, effectively reduce outside water, the erosion of oxygen isoreactivity material to organic electroluminescence device, make up the shortcoming on single sulfurized layer and single organic substance barrier layer, extended device lifetime.
Method by vacuum evaporation is prepared protective layer on cathode layer, and the existence of protective layer can protect negative electrode to exempt from destruction in subsequent operation process.
Preferably, when the method for employing vacuum evaporation is prepared protective layer, vacuum degree is 3 × 10
-5～8 × 10
-5pa, evaporation rate is
Functional layer generally includes hole injection layer, hole transmission layer, electron transfer layer and electron injecting layer.Luminescent layer is arranged between hole transmission layer and electron transfer layer.Preferably, functional layer and luminescent layer are the method setting by vacuum evaporation.
Containing aluminium polyethylene terephthalate film edge-coating epoxy encapsulation glue, by the dry sclerosis of the mode packaging plastic of ultraviolet curing, described organic electroluminescence device is encapsulated in described containing in aluminium polyethylene terephthalate film and substrate.
Preferably, while being cured with UV light (λ=365nm), light intensity is 10～15mW/cm
2, the time for exposure is 300～400s.
The invention provides a kind of organic electroluminescence device and preparation method thereof and there is following beneficial effect:
(1) organic electroluminescence device of the present invention can reduce outside water, the erosion of oxygen isoreactivity material to organic electroluminescence device effectively, thereby device organic functional material and electrode are formed to effective protection, improve significantly the life-span of organic electroluminescence device;
(2) organic electroluminescence device water resistance of the present invention (WVTR) reaches 4.5E
-5g/m
2day, the life-span reaches more than 11,000 hours;
(3) the inventive method is applicable to the organic electroluminescence device prepared take electro-conductive glass as anode substrate of encapsulation, is also applicable to the flexible organic electroluminescent device that encapsulation is prepared as anode substrate take plastics or metal; The inventive method is particularly useful for encapsulating flexible organic electroluminescent device;
(4) organic electroluminescence device material cheapness of the present invention, method for packing mode is simple, and easily large area preparation is suitable for large-scale industrialization and uses.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic electroluminescence device of the present invention.
Embodiment
The following stated is the preferred embodiment of the present invention.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvement and adjustment, these improvement and adjustment are also considered as in protection scope of the present invention.
Embodiment 1:
A preparation method for organic electroluminescence device, comprises the following steps:
(1) ITO conducting glass substrate 1 pre-treatment: ITO conducting glass substrate 1 is put into acetone, ethanol, deionized water, ethanol successively, and ultrasonic cleaning 5 minutes, then dries up with nitrogen respectively, and stove-drying is stand-by; Ito glass substrate 1 after cleaning is carried out to surface activation process, to increase the oxygen content of conductive surface layer, improve the work function of conductive layer surface; ITO conducting glass substrate 1 thickness is 100nm;
(2) preparation of functional layer and luminescent layer:
Hole injection layer 2: evaporation MoO on ITO conducting glass substrate 1
3the composite material that doping NPB obtains, MoO
3doping mass fraction be 25%, evaporation all adopts high vacuum coating equipment to carry out, when evaporation, vacuum degree is 3 × 10
-5pa, evaporation rate is
obtain hole injection layer 2, thickness is 10nm;
Hole transmission layer 3: adopt 4,4', 4 " tri-(carbazole-9-yl) triphenylamine (TCTA) is as hole mobile material, evaporation TCTA on hole injection layer 2, vacuum degree is 3 × 10
-5pa, evaporation rate is
evaporation thickness is 40nm;
Luminescent layer 4: evaporation luminescent layer 4 on hole transmission layer 3, luminescent layer 4 material of main parts adopt 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), guest materials adopts three (2-phenylpyridines) to close iridium (Ir (ppy)
3), guest materials quality accounts for 5% of material of main part, and vacuum degree is 3 × 10
-5pa, evaporation rate is
evaporation thickness is 20nm;
The preparation of electron transfer layer 5: evaporation 4 on luminescent layer 4,7-diphenyl-1,10-phenanthroline (Bphen) is as electron transport material, and vacuum degree is 3 × 10
-5pa, evaporation rate is
evaporation thickness is 30nm;
The preparation of electron injecting layer 6: evaporation electron injection material forms electron injecting layer 6 on electron transfer layer 5, and electron injecting layer 6 materials are CsN
3doping Bphen, doping mass fraction is 25%, vacuum degree is 3 × 10
-5pa, evaporation rate is
evaporation thickness is 20nm;
(3) preparation of cathode layer 7: evaporation metal negative electrode 7 on electron injecting layer 6, metallic cathode 7 adopts aluminium (Al), and thickness is 100nm, and evaporation vacuum degree is 5 × 10
-5pa, evaporation rate is
(4) preparation of protective layer 801: adopt the method for vacuum evaporation to prepare CuPc on cathode layer 7, vacuum degree is 3 × 10
-5pa, evaporation rate is
thickness is 200nm;
(5) preparation on barrier layer:
(a) preparation of the first sulfurized layer 802: the material that the method for employing reaction magnetocontrol sputtering is prepared the first sulfurized layer 802, the first sulfurized layers on protective layer 801 is WS
2, sputtering target material is W, passes into the mist that gas is hydrogen sulfide and argon gas, and gas flow is 10sccm, and the volume fraction that hydrogen sulfide accounts for mist is 3%, and base vacuum degree is 1 × 10
-3pa, thickness is 150nm;
(b) preparation of the second sulfurized layer 803: the material that adopts the method for non-reaction magnetocontrol sputtering to prepare the second sulfurized layer 803, the second sulfurized layers on the first sulfurized layer 802 is WS
2, sputtering target material is WS
2, passing into gas is argon gas, and gas flow is 10sccm, and base vacuum degree is 1 × 10
-3pa, thickness is 150nm;
(c) preparation on organic barrier layer 804: adopt the method for first spin coating post-exposure to prepare organic barrier layer 804 on the second sulfurized layer 803, the material on organic barrier layer 804 is polytetrafluoroethylene, under inert atmosphere, make, gluing thickness is 1.5 μ m, then be cured with UV light (λ=365nm), light intensity is 15mW/cm
2, the time for exposure is 200s;
(d) the first sulfurized layer 805, 808, 811, the second sulfurized layer 806, 809, 812 and organic barrier layer 807, 810, 813 preparation: adopt method and the material identical with step (a) to prepare the first sulfurized layer 805 after step (c) on organic barrier layer 804, on the first sulfurized layer 805, adopt again method and the material that step (b) is identical to prepare the second sulfurized layer 806, on the second sulfurized layer 806, adopt method and the material identical with step (c) to prepare organic barrier layer 807, on organic barrier layer 807, adopt method and the material that step (a) is identical to prepare the first sulfurized layer 808, on the first sulfurized layer 808, adopt method and the material identical with step (b) to prepare the second sulfurized layer 809, on the second sulfurized layer 809, adopt method and the material that step (c) is identical to prepare organic barrier layer 810, on organic barrier layer 810, adopt method and the material that step (a) is identical to prepare the first sulfurized layer 811, on the first sulfurized layer 811, adopt method and the material identical with step (b) to prepare the second sulfurized layer 812, on the second sulfurized layer 812, adopt method and the material that step (c) is identical to prepare organic barrier layer 813, finally obtain the barrier layer of containing 4 layers of basic structure.
(6) containing the covering of aluminium PET film 814: containing aluminium PET film 814 edge-coating packaging plastics, be cured light intensity 15mW/cm with UV light (λ=365nm)
2, time for exposure 300s; Organic electroluminescence device is encapsulated in containing in aluminium PET film 814 and glass substrate 1.
Water oxygen permeability (WVTR, the g/m of the present embodiment organic electroluminescence device
2day) be 4.7E
-5, the life-span of organic electroluminescence device is 1,1489h(T70@1000cd/m
2).
Fig. 1 is the structural representation of the organic electroluminescence device that makes of the embodiment of the present invention 1.As shown in Figure 1, the present embodiment organic electroluminescence device, comprise successively ITO conducting glass substrate 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6, cathode layer 7 and encapsulated layer 8, encapsulated layer 8 comprises protective layer 801, 4 layer of first sulfurized layer 802, 805, 808, 811, 4 layer of second sulfurized layer 803, 806, 809, 812, 4 layers of organic barrier layer 804, 807, 810, 813 and containing aluminium PET film 814, ITO conducting glass substrate 1 and containing aluminium PET film 814 by packaging plastic seal formation enclosure space, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6, cathode layer 7, protective layer 801, the first sulfurized layer 802, 805, 808, 811, the second sulfurized layer 803, 806, 809, 812, organic barrier layer 804, 807, 810, 813 are contained in this enclosure space.
Embodiment 2:
A preparation method for organic electroluminescence device, comprises the following steps:
(1), (2), (3) are with embodiment 1;
(4) preparation of protective layer: adopt the method for vacuum evaporation to prepare NPB on cathode layer, vacuum degree is 5 × 10
-5pa, evaporation rate is
thickness is 300nm;
(5) preparation on barrier layer:
(a) preparation of the first sulfurized layer: adopt the method for reaction magnetocontrol sputtering to prepare the first sulfurized layer on protective layer, the material of the first sulfurized layer is MoS
2, sputtering target material is Mo, and passing into gas is hydrogen sulfide and argon gas, and the volume fraction that hydrogen sulfide accounts for mist is 17%, and gas flow is 15sccm, base vacuum degree is 2 × 10
-4pa, thickness is 100nm;
(b) preparation of the second sulfurized layer: adopt the method for non-reaction magnetocontrol sputtering to prepare the second sulfurized layer on the first sulfurized layer, the material of the second sulfurized layer is MoS
2, sputtering target material is MoS
2, passing into gas is argon gas, and gas flow is 15sccm, and base vacuum degree is 2 × 10
-4pa, thickness is 100nm;
(c) preparation on organic barrier layer: adopt the method for first spin coating post-exposure to prepare organic barrier layer on the second sulfurized layer, the material on organic barrier layer is methacrylic resin, under inert atmosphere, make, gluing thickness 1 μ m, then be cured light intensity 10mW/cm with UV light (λ=365nm)
2, time for exposure 150s;
(d) after step (c), adopt method and the material identical with step (a) on organic barrier layer, to prepare the first sulfurized layer, on the first sulfurized layer, adopt again method and the material that step (b) is identical to prepare the second sulfurized layer, on the second sulfurized layer, adopt method and the material identical with step (c) to prepare organic barrier layer, the first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, prepare multiple basic structure and repeat to form barrier layer, finally obtain the barrier layer of containing 4 layers of basic structure;
(6) containing the covering of aluminium PET film: containing aluminium PET film edge coating packaging plastic, be cured light intensity 10mW/cm with UV light (λ=365nm)
2, time for exposure 400s; Organic electroluminescence device is encapsulated in containing in aluminium PET film and glass substrate.
Water oxygen permeability (WVTR, the g/m of the present embodiment organic electroluminescence device
2day) be 5.2E
-5, the life-span of organic electroluminescence device is 1,1124h(T70@1000cd/m
2).
Embodiment 3:
A preparation method for organic electroluminescence device, comprises the following steps:
(1), (2), (3) are with embodiment 1;
(4) preparation of protective layer: adopt the method for vacuum evaporation to prepare Alq on cathode layer
3, vacuum degree is 8 × 10
-5pa, evaporation rate is
thickness is 250nm;
(5) preparation on barrier layer:
(a) preparation of the first sulfurized layer: adopt the method for reaction magnetocontrol sputtering to prepare the first sulfurized layer on protective layer, the material of the first sulfurized layer is TaS
2, sputtering target material is Ta, and passing into gas is hydrogen sulfide and argon gas, and the volume fraction that hydrogen sulfide accounts for mist is 10%, and gas flow is 12sccm, base vacuum degree is 1 × 10
-5pa, thickness is 120nm;
(b) preparation of the second sulfurized layer: adopt the method for non-reaction magnetocontrol sputtering to prepare the second sulfurized layer on the first sulfurized layer, the material of the second sulfurized layer is TaS
2, sputtering target material is TaS
2, passing into gas is argon gas, and gas flow is 11sccm, and base vacuum degree is 1 × 10
-5pa, thickness is 120nm;
(c) preparation on organic barrier layer: adopt the method for first spin coating post-exposure to prepare organic barrier layer on the second sulfurized layer, the material on organic barrier layer is methacrylic resin, under inert atmosphere, make, gluing thickness is 1.2 μ m, then be cured with UV light (λ=365nm), light intensity is 12mW/cm
2, the time for exposure is 180s;
(d) after step (c), adopt method and the material identical with step (a) on organic barrier layer, to prepare the first sulfurized layer, on the first sulfurized layer, adopt again method and the material that step (b) is identical to prepare the second sulfurized layer, on the second sulfurized layer, adopt method and the material identical with step (c) to prepare organic barrier layer, the first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, prepare multiple basic structure and repeat to form barrier layer, finally obtain the barrier layer containing the basic structure that is of five storeys;
(6) containing the covering of aluminium PET film: containing aluminium PET film edge coating packaging plastic, be cured light intensity 12mW/cm with UV light (λ=365nm)
2, time for exposure 350s; Organic electroluminescence device is encapsulated in containing in aluminium PET film and glass substrate.
Water oxygen permeability (WVTR, the g/m of the present embodiment organic electroluminescence device
2day) be 6.3E
-5, the life-span of organic electroluminescence device is 1,1037h(T70@1000cd/m
2).
Embodiment 4:
A preparation method for organic electroluminescence device, comprises the following steps:
(1), (2), (3) are with embodiment 1;
(4) preparation of protective layer: adopt the method for vacuum evaporation to prepare SiO on cathode layer, vacuum degree is 5 × 10
-5pa, evaporation rate is
thickness is 300nm;
(5) preparation on barrier layer:
(a) preparation of the first sulfurized layer: adopt the method for reaction magnetocontrol sputtering to prepare the first sulfurized layer on protective layer, the material of the first sulfurized layer is NbS
2, sputtering target material is Nb, and passing into gas is hydrogen sulfide and argon gas, and the volume fraction that hydrogen sulfide accounts for mist is 10%, and gas flow is 11sccm, base vacuum degree is 2 × 10
-4pa, thickness is 120nm;
(b) preparation of the second sulfurized layer: adopt the method for non-reaction magnetocontrol sputtering to prepare the second sulfurized layer on the first sulfurized layer, the material of the second sulfurized layer is NbS
2, sputtering target material is NbS
2, passing into gas is argon gas, and gas flow is 11sccm, and base vacuum degree is 2 × 10
-4pa, thickness is 120nm;
(c) preparation on organic barrier layer: adopt the method for first spin coating post-exposure to prepare organic barrier layer on the second sulfurized layer, the material on organic barrier layer is methacrylic resin, under inert atmosphere, make, gluing thickness is 1.2 μ m, then be cured with UV light (λ=365nm), light intensity is 13mW/cm
2, the time for exposure is 190s;
(d) after step (c), adopt method and the material identical with step (a) on organic barrier layer, to prepare the first sulfurized layer, on the first sulfurized layer, adopt again method and the material that step (b) is identical to prepare the second sulfurized layer, on the second sulfurized layer, adopt method and the material identical with step (c) to prepare organic barrier layer, the first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, prepare multiple basic structure and repeat to form barrier layer, finally obtain the barrier layer of containing 4 layers of basic structure;
(6) containing the covering of aluminium PET film: containing aluminium PET film edge coating packaging plastic, be cured with UV light (λ=365nm), light intensity is 15mW/cm
2, the time for exposure is 300s; Organic electroluminescence device is encapsulated in containing in aluminium PET film and glass substrate.
Water oxygen permeability (WVTR, the g/m of the present embodiment organic electroluminescence device
2day) be 5.0E
-5, the life-span of organic electroluminescence device is 1,1243h(T70@1000cd/m
2).
Embodiment 5:
A preparation method for organic electroluminescence device, comprises the following steps:
(1), (2), (3) are with embodiment 1;
(4) preparation of protective layer: adopt the method for vacuum evaporation to prepare MgF on cathode layer
2, vacuum degree is 5 × 10
-5pa, evaporation rate is
thickness is 300nm;
(5) preparation on barrier layer:
(a) preparation of the first sulfurized layer: adopt the method for reaction magnetocontrol sputtering to prepare the first sulfurized layer on protective layer, the material of the first sulfurized layer is Sb
2s
3, sputtering target material is Sb, and passing into gas is hydrogen sulfide and Ar, and the volume fraction that hydrogen sulfide accounts for mist is 10%, and gas flow is 12sccm, base vacuum degree is 2 × 10
-4pa, thickness is 120nm;
(b) preparation of the second sulfurized layer: adopt the method for non-reaction magnetocontrol sputtering to prepare the second sulfurized layer on the first sulfurized layer, the material of the second sulfurized layer is Sb
2s
3, sputtering target material is Sb
2s
3, passing into gas is Ar, and gas flow is 12sccm, and base vacuum degree is 2 × 10
-4pa, thickness is 120nm;
(c) preparation on organic barrier layer: adopt the method for first spin coating post-exposure to prepare organic barrier layer on the second sulfurized layer, the material on organic barrier layer is methacrylic resin, under inert atmosphere, make, gluing thickness 1.2 μ m, then be cured light intensity 13mW/cm with UV light (λ=365nm)
2, time for exposure 190s;
(d) after step (c), adopt method and the material identical with step (a) on organic barrier layer, to prepare the first sulfurized layer, on the first sulfurized layer, adopt again method and the material that step (b) is identical to prepare the second sulfurized layer, on the second sulfurized layer, adopt method and the material identical with step (c) to prepare organic barrier layer, the first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, prepare multiple basic structure and repeat to form barrier layer, finally obtain the barrier layer of containing 7 layers of basic structure;
(6) containing the covering of aluminium PET film: containing aluminium PET film edge coating packaging plastic, be cured with UV light (λ=365nm), light intensity is 15mW/cm
2, the time for exposure is 300s; Organic electroluminescence device is encapsulated in containing in aluminium PET film and glass substrate.
Water oxygen permeability (WVTR, the g/m of the present embodiment organic electroluminescence device
2day) be 4.5E
-5, the life-span of organic electroluminescence device is 1,1871h(T70@1000cd/m
2).
Embodiment 6:
A preparation method for organic electroluminescence device, comprises the following steps:
(1), (2), (3) are with embodiment 1;
(4) preparation of protective layer: adopt the method for vacuum evaporation to prepare ZnS on cathode layer, vacuum degree is 5 × 10
-5pa, evaporation rate is
thickness is 250nm;
(5) preparation on barrier layer:
(a) preparation of the first sulfurized layer: adopt the method for reaction magnetocontrol sputtering to prepare the first sulfurized layer on protective layer, the material of the first sulfurized layer is As
2s
3, sputtering target material is As, and passing into gas is hydrogen sulfide and Ar, and the volume fraction that hydrogen sulfide accounts for mist is 6%, and gas flow is 14sccm, base vacuum degree is 2 × 10
-4pa, thickness is 120nm;
(b) preparation of the second sulfurized layer: adopt the method for non-reaction magnetocontrol sputtering to prepare the second sulfurized layer on the first sulfurized layer, the material of the second sulfurized layer is As
2s
3, sputtering target material is As
2s
3, passing into gas is Ar, and gas flow is 14sccm, and base vacuum degree is 2 × 10
-4pa, thickness is 120nm;
(c) preparation on organic barrier layer: adopt the method for first spin coating post-exposure to prepare organic barrier layer on the second sulfurized layer, the material on organic barrier layer is methacrylic resin, under inert atmosphere, make, gluing thickness is 1.2 μ m, then be cured with UV light (λ=365nm), light intensity is 12mW/cm
2, the time for exposure is 150s;
(d) after step (c), adopt method and the material identical with step (a) on organic barrier layer, to prepare the first sulfurized layer, on the first sulfurized layer, adopt again method and the material that step (b) is identical to prepare the second sulfurized layer, on the second sulfurized layer, adopt method and the material identical with step (c) to prepare organic barrier layer, the first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, prepare multiple basic structure and repeat to form barrier layer, finally obtain the barrier layer of containing 4 layers of basic structure;
(6) containing the covering of aluminium PET film: with containing aluminium PET film edge coating packaging plastic, be cured with UV light (λ=365nm), light intensity is 15mW/cm
2, the time for exposure is 300s; Organic electroluminescence device is encapsulated in containing in aluminium PET film and glass substrate.
Water oxygen permeability (WVTR, the g/m of the present embodiment organic electroluminescence device
2day) be 5.9E
-5, the life-span of organic electroluminescence device is 1,1118h(T70@1000cd/m
2).
Effect embodiment
For the beneficial effect of valid certificates organic electroluminescence device of the present invention and preparation method thereof, provide related experiment data as follows.
Table 1 is embodiment 1 ~ 6 organic electroluminescence device water oxygen permeability, and table 2 is embodiment 1 ~ 6 organic electro-luminescence device lifetime situations.
Table 1. embodiment 1 ~ 6 organic electroluminescence device water oxygen permeability
| Embodiment 1 | Embodiment 2 | |
|
Embodiment 5 | Embodiment 6 | |
| WVTR(g/m 2/day) | 4.7E -5 | 5.2E -5 | 6.3E -5 | 5.0E -5 | 4.5E -5 | 5.9E -5 |
Table 2. embodiment 1 ~ 6 organic electro-luminescence device lifetime situation
As can be seen from Table 1, the water oxygen permeability of organic electroluminescence device of the present invention (WVTR) reaches 4.5E
-5g/m
2day, as can be seen from Table 2, the life-span of organic electroluminescence device of the present invention reaches 1,1037 hour above (T70@1000cd/m
2).
To sum up; organic electroluminescence device provided by the invention can reduce outside water, the erosion of oxygen isoreactivity material to organic electroluminescence device effectively; thereby device organic functional material and electrode are formed to effective protection; meet the sealing requirements of encapsulation, the life-span that can improve significantly OLED device.
Claims (10)
1. an organic electroluminescence device, comprise the anode conducting substrate, functional layer, luminescent layer, cathode layer and the encapsulated layer that stack gradually, anode conducting substrate and encapsulated layer form enclosure space, functional layer, luminescent layer and cathode layer are contained in this enclosure space, it is characterized in that, described encapsulated layer comprises successively protective layer, barrier layer and contains aluminium polyethylene terephthalate film;
Described barrier layer comprises the first sulfurized layer, the second sulfurized layer and organic barrier layer successively;
Described the first sulfurized layer is identical with the second sulfurized layer material, is tungsten disulfide, molybdenum bisuphide, tantalum disulfide, curing niobium, antimonous sulfide or orpiment;
The material on described organic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin.
2. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the first sulfurized layer is 100～150nm.
3. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness of described the second sulfurized layer is 100～150nm.
4. organic electroluminescence device as claimed in claim 1, is characterized in that, the thickness on described organic barrier layer is 1～1.5 μ m.
5. organic electroluminescence device as claimed in claim 1, is characterized in that, described the first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, and described barrier layer is that 4～7 basic structures repeat to form.
6. a preparation method for organic electroluminescence device, is characterized in that, comprises the following steps:
(1) on clean conducting glass substrate or conduction organic film substrate, be prepared with the anode pattern of organic electroluminescence devices; Adopt the method for vacuum evaporation on anode conducting substrate, to prepare successively functional layer, luminescent layer, cathode layer and protective layer;
(2) preparation method on barrier layer is as follows:
(a) adopt the method for reaction magnetocontrol sputtering on protective layer, to prepare the first sulfurized layer, the material of described the first sulfurized layer is tungsten disulfide, molybdenum bisuphide, tantalum disulfide, curing niobium, antimonous sulfide or orpiment;
(b) adopt the method for non-reaction magnetocontrol sputtering on protective layer, to prepare the second sulfurized layer, the material of described the second sulfurized layer is tungsten disulfide, molybdenum bisuphide, tantalum disulfide, curing niobium, antimonous sulfide or orpiment;
(c) adopt the method for first spin coating post-exposure on sulfurized layer, to prepare organic barrier layer, the material on described organic barrier layer is polytetrafluoroethylene, methacrylic resin or cycloaliphatic epoxy resin;
(3), containing aluminium polyethylene terephthalate film edge-coating epoxy encapsulation glue, by the dry sclerosis of the mode packaging plastic of ultraviolet curing, described organic electroluminescence device is encapsulated in described containing in aluminium polyethylene terephthalate film and substrate.
7. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, while adopting reaction magnetocontrol sputtering to prepare described the first sulfurized layer, sputtering target material is tungsten, molybdenum, tantalum, niobium, antimony or arsenic, pass into the mist that gas is hydrogen sulfide and argon gas, the volume fraction that described hydrogen sulfide accounts for mist is 3% ~ 17%, and when sputter, base vacuum degree is 1 × 10
-5～1 × 10
-3pa.
8. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, while adopting non-reaction magnetocontrol sputtering to prepare described the second sulfurized layer, sputtering target material is tungsten disulfide, molybdenum bisuphide, tantalum disulfide, curing niobium, antimonous sulfide or orpiment, passing into gas is argon gas, and when sputter, base vacuum degree is 1 × 10
-5～1 × 10
-3pa.
9. the preparation method of organic electroluminescence device as claimed in claim 6, is characterized in that, under inert atmosphere, behind the organic barrier layer of spin coating, is cured with UV light, and light intensity is 10～15mW/cm
2, the time for exposure is 150～200s.
10. the preparation method of organic electroluminescence device as claimed in claim 6, it is characterized in that, after step (c), adopt method and the material identical with step (a) on organic barrier layer, to prepare the first sulfurized layer, on described the first sulfurized layer, adopt again method and the material that step (b) is identical to prepare the second sulfurized layer, on the second described sulfurized layer, adopt method and the material identical with step (c) to prepare organic barrier layer, described the first sulfurized layer, the second sulfurized layer and organic barrier layer form a basic structure, prepare 4～7 described basic structures and repeat the barrier layer forming.
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| CN101080121A (en) * | 2007-07-06 | 2007-11-28 | 清华大学 | An organic EL part and its making method |
| US20090215279A1 (en) * | 2008-02-25 | 2009-08-27 | Korea Institute Of Science And Technology | Organic/inorganic hybrid thin film passivation layer for blocking moisture/oxygen transmission and improving gas barrier property |
| CN102214803A (en) * | 2011-05-20 | 2011-10-12 | 电子科技大学 | Packaging method of photoelectronic device |
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| CN1452437A (en) * | 2002-04-17 | 2003-10-29 | 朱星厚 | Method for mfg. organic electroluminescent display panel covered with protective film |
| CN101080121A (en) * | 2007-07-06 | 2007-11-28 | 清华大学 | An organic EL part and its making method |
| US20090215279A1 (en) * | 2008-02-25 | 2009-08-27 | Korea Institute Of Science And Technology | Organic/inorganic hybrid thin film passivation layer for blocking moisture/oxygen transmission and improving gas barrier property |
| CN102214803A (en) * | 2011-05-20 | 2011-10-12 | 电子科技大学 | Packaging method of photoelectronic device |
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Application publication date: 20140611 |