CN100553013C - A kind of organic electroluminescence device - Google Patents
A kind of organic electroluminescence device Download PDFInfo
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- CN100553013C CN100553013C CNB200710105977XA CN200710105977A CN100553013C CN 100553013 C CN100553013 C CN 100553013C CN B200710105977X A CNB200710105977X A CN B200710105977XA CN 200710105977 A CN200710105977 A CN 200710105977A CN 100553013 C CN100553013 C CN 100553013C
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- encapsulating structure
- electroluminescence device
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- drier
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Abstract
The present invention relates to a kind of organic electroluminescence device of flexibility, by the life-span that moisturizes and the absorbent properties of oxygen are improved soft screen.Organic electroluminescence device of the present invention comprises encapsulating structure, this encapsulating structure comprises the thick film layers that one deck is formed by polymeric material, be doped with drier in the thick film layers, drier is selected from least a of alkali metal, alkaline-earth metal and metal oxide, zeolite, the metal alcoholate with long-chain hydrocarbon, sulfate, halide, perchlorate.Encapsulating structure is positioned at the one or both sides of flexible organic electroluminescent device among the present invention.Adopt encapsulating structure of the present invention to simplify the preparation technology of encapsulation, reduced the defective in the preparation process simultaneously, improved the pliability and the water and oxygen barrier property of device, the life-span of having improved device.
Description
Technical field
The present invention relates to encapsulating structure of a kind of flexible organic electroluminescent device and preparation method thereof, belong to technical field of organic electroluminescence.
Background technology
Now, along with the arriving of Development of Multimedia Technology and information-intensive society, more and more higher to the flat-panel monitor performance demands.A series of advantages such as display of organic electroluminescence (OLEDs) has from main light emission, low-voltage DC driven, solidifies entirely, the visual angle is wide, color is abundant, compare with LCD, OLEDs does not need backlight, the visual angle is big, power is low, its response speed can reach 1000 times of LCD, and its manufacturing cost but is lower than the LCD of equal resolution.Therefore, OLEDs has broad application prospects, and is counted as the utmost point and composes one of following flat panel display of competitiveness.Nowadays, OLEDs is as a kind of display device (no matter being micromolecule or polymer) of full curing, its prime advantage is to prepare flexible display device, flexible organic electroluminescent device refers to the flexible material to be the organic electroluminescence device of substrate, because the characteristics of flexible substrate have given unique application prospect just for this class device, as the display device of flexibility, flexible e-newspaper, the wallpaper TV, wearable display etc.
Flexible OLEDs only is the different of substrate with the different of common OLEDs, but for soft screen device, substrate is the main cause that influences its efficient and life-span.The plastic substrate that soft screen device adopts is compared with glass substrate, and following shortcoming is arranged:
(1) planarization of plastic substrate is usually than glass substrate difference, and the projection of substrate surface brings defective can for the device film layer structure, causes device failure;
(2) water of plastic substrate, oxygen permeability are higher than glass substrate far away, and water, oxygen are the principal elements that causes device aging rapidly.Even the film of the band water oxygen barrier layer of using in fields such as packagings for foodstuff, its water oxygen permeability also greatly differ from each other with the requirement of OLEDs.
The OLEDs product is technical from volume production, does not also reach the requirement of commercialization at present, and the life-span is one of greatest problem that faces at present.We can say that the life problems of OLEDs can not get corresponding solution, the commercialization and the practicability of the display of a new generation are not just known where to begin.At present, because organic substance in the device and negative electrode are all very responsive to steam and oxygen, the life problems of OLEDs depends on the quality of device package effect to a great extent in other words.A large amount of studies show that steam and oxygen are the main causes that cause OLEDs to lose efficacy, and are easy to and steam, oxygen reaction as the active metal of OLEDs negative electrode.We can do a simple estimation, and the atomic weight of Mg is 24, and density is 1.74g/cm
3If the thickness of the metallic cathode Mg layer among the OLEDs is 50nm, then the amount of this device containing metal Mg is 3.6 * 10
-7Mol/cm
2, only need about 6.4 * 10
-6G water is complete reaction with it just.Make that the complete destroyed time of Mg is 1 year, then encapsulated layer must make the water permeability less than 1.5 * 10
-4G/m
2/ day.As long as and in fact in the device negative electrode have 10% oxidizedly, the not light-emitting zone of formation is just very obviously (if the oxidation of negative electrode occurs in metal and at the interface organic, even ruined negative electrode only is
Also may cause component failure), it has been generally acknowledged that ignore the destruction to organic layer of water, oxygen, the encapsulated layer water oxygen permeability that OLEDs requires should be less than 10
-5G/m
2/ day (Burrows PE, Graff GL, Gross ME, et al.Displays 22,652001).
The method for packing of glass cover, crown cap is generally adopted in the encapsulation of organic electroluminescence device in the prior art, and its edge is resin-sealed with ultraviolet polymerization.Because glass cover, crown cap are dense, therefore the method for this encapsulation can fine obstruct water oxygen to the seepage of device inside, well prolonged the useful life of device.This method has its corresponding shortcoming, and is big as volume, increased the weight of device.
Another one shortcoming with glass cover or crown cap encapsulation is the encapsulation that can not be applied to flexible OLEDs.The method of the bonding case chip that OLEDs adopted of glass substrate is not suitable for soft screen, because soft screen device is when bending, and the bonding case chip destruction metal level that might rub.Thereby it is its main trend that develops in the future that flexible OLEDs abandons the encapsulation of hard screen cap employing thin and thick film.For this reason, people have carried out modification to plastic substrate, improve the surface smoothness of plastic substrate, improve its water and oxygen barrier property.U.S. Pat 4,842, on June 27th, 1989), US4 the 893 (days for announcing:, 954, September 4 nineteen ninety) and US5 the 371 (days for announcing:, 260,095 (day for announcing: polymer alternate multi-layered film (Polymer Multilayer is hereinafter to be referred as the PML) technology of on November 9th, 1993) mentioning is considered to an effective technology of improving the plastic substrate performance.The PML technology is the alternate multi-layered film for preparing polymeric material, ceramic-like materials under vacuum state.Wherein polymeric layer is as the resilient coating of flexibility, and plays the effect that makes plastic substrate surfacing homogeneous.The polymeric material that adopts be the polymer monomer of liquid state under the room temperature normally, as acrylic monomer, evaporation because surface tension effects forms very smooth rete, makes it polymerizing curable by UV-irradiation again behind substrate surface, form the polyacrylate rete.The ceramic-like materials that adopts is silica, silicon nitride, silicon oxynitride and aluminium oxide, aluminium nitride, aluminum oxynitride etc. normally, and the water oxygen permeability is extremely low, and transparent at visible region.Studies show that the plastic substrate surface after the modification of PML technology is very smooth, and water and oxygen barrier property can match in excellence or beauty with glassy phase.The introducing of PML alternating multilayered structure has also improved the adhesion of plastic substrate and nesa coating (as tin indium oxide, hereinafter to be referred as ITO), thereby improves the performance of OLEDs.
The PML technology also can be used for the encapsulation of OLEDs.This encapsulation technology can match in excellence or beauty with glassy phase to the obstructing capacity of water oxygen.Become the main flow of flexible organic electroluminescent device encapsulation.But the PML technology is owing to need the polymer and the ceramic-like materials in a plurality of cycles of preparation, technology, equipment are all very complicated, ceramic-like materials particularly, the general methods such as magnetron sputtering, plasma enhanced chemical gaseous phase deposition that adopt prepare, temperature is higher in the preparation process, destroy organic layer or metal electrode easily, and when object is bent, the material (as ceramic material) of bending ability comes off easily, and follow the mechanism of " tunnelling-layering-protuberance-fracture ", influence the life-span and the mechanical performance of device.
Technology (US6146225, the Agilent Technology that drier is used for encapsulated layer also arranged at present; US6888307, UDC; CN1705419, Hitachi shows) but drier all is to be placed in the encapsulated layer of alternate multiple as one deck separately usually, and this mode adopts vacuum deposition method to prepare more, and drier can increase operation for one deck separately, makes complex process, and is consuming time more.
In the prior art also the handlebar drier be entrained in the device substrate (US6465953 GE), allows drier and encapsulated layer use together to play and strengthens dry effect.But this method can increase the degree of difficulty of substrate storage, is not suitable for producing practical.
Summary of the invention
For addressing the above problem, the invention provides a kind of flexible organic electroluminescent device that comprises novel package structure, to improve the life-span and the mechanical performance of device.
The present invention proposes a kind of flexible organic electroluminescent device, comprises encapsulating structure, comprises the thick film layers that is formed by polymeric material in the encapsulating structure, it is characterized in that, contains drier in the described thick film layers.
Drier in the organic electroluminescence device of the present invention is the material of granular, wire, spherical or sheet, and drier is of a size of 10nm～10 μ m, and drier shared volume percent content in thick film layers is 10%～60%.
In the organic electroluminescence device of the present invention, encapsulating structure is positioned at the one or both sides of device.The substrate of device is a flexible substrates.
Organic electroluminescence device of the present invention, the drier in the encapsulating structure be selected from alkaline-earth metal, alkaline earth oxide, zeolite, have in the metal alcoholate of long-chain hydrocarbon, sulfate, halide, perchlorate at least a.
Organic electroluminescence device of the present invention, the drier in the encapsulating structure is selected from sodium, calcium, magnesium, barium, lithia, sodium oxide molybdena, potassium oxide, barium monoxide, calcium oxide, magnesium oxide, lithium sulfate, sodium sulphate, calcium sulfate, magnesium sulfate, sulfuric acid bores, gallium sulfate, titanium sulfate, nickelous sulfate, calcium chloride, magnesium chloride, cesium chloride, strontium chloride, beryllium chloride, yttrium chloride, copper chloride, gallium chloride, cesium fluoride, stannous fluoride, antimony fluoride, fluoridize tantalum, fluoridize niobium, lithium bromide, calcium bromide, comprise cerium bromide, selenium bromide, the bromination vanadium, magnesium bromide, barium iodide, magnesium iodide, at least a in barium perchlorate and the magnesium perchlorate.
Polymeric material in the encapsulating structure is preferably thermoset plastics, UV and solidifies a kind of in the glue etc.Be preferably a kind of in phenolic resins, Lauxite, melmac, unsaturated polyester resin, epoxy resin, organic siliconresin, polyurethane, polymethyl methacrylate, polyethyl methacrylate, the UV cured resin.The thickness of the thick film layers in the encapsulating structure is 10 μ m～1000 μ m.
Also comprise the stainless steel foil lamella in the encapsulating structure.
The alternate multi-layered film that also comprises organic inorganic compounding in the encapsulating structure.
The organic electroluminescence device that comprises encapsulating structure that the present invention proposes has the following advantages: the size of drier and volume percent content can be regulated and control voluntarily to satisfy the requirement of device to light transmission.When the exit direction of light when having this side of encapsulating structure, in order not influence the light transmission of substrate or transparency electrode, the size of drier and volume content can be less; When the exit direction of light was the relative side of encapsulating structure, the size of drier and volume content can be bigger, to guarantee better packaging effect.
When preparing encapsulating structure of the present invention, can directly thick film layers be coated on the device and encapsulate, such once going on foot the dual-use function that can reach exclusion of water oxygen and absorb water oxygen, greatly simplified preparation technology, reduced the defective in the device preparation process simultaneously, improve the pliability and the water and oxygen barrier property of device, and then improved the life-span and the mechanical performance of device.
Be illustrated by embodiment, embodiment below in conjunction with accompanying drawing, it is clearer that the present invention can become.
Description of drawings
The device architecture schematic diagram of Fig. 1 embodiment of the invention 1.
The device architecture schematic diagram of Fig. 2 embodiment of the invention 3.
The device architecture schematic diagram of Fig. 3 embodiment of the invention 4.
Brightness decay curve when Fig. 4 is the embodiment of the invention 3 encapsulation and Comparative Examples 1 packaged device continuous firing.
Elaborate content of the present invention below in conjunction with the drawings and specific embodiments, should be appreciated that the present invention is not limited to following preferred implementation, preferred implementation is as just illustrative embodiment of the present invention.
Embodiment
(1) preparation of anode layer: substrate is a flexible substrate, deposition anode layer on the substrate.Anode can adopt inorganic material or organic conductive polymer, inorganic material is generally the higher metals of work function such as metal oxides such as tin indium oxide (ITO), zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as, usually the square resistance of ITO film is 50 Ω, thickness is generally 150nm, and the organic conductive polymer is preferably a kind of material in polythiophene/polyvinylbenzenesulfonic acid sodium (PEDOT:PSS), the polyaniline (PANI);
(2) be carved with the cleaning of the substrate of anode in advance: utilize alkali lye spray and the ultrasonic method of deionized water that the electrically conducting transparent flexible substrate is cleaned, place it in oven dry under the infrared lamp after the cleaning, the substrate to oven dry carries out the preliminary treatment that UV ozone is cleaned and the low energy oxygen ion beam bombards then;
(3) preparation of organic function layer: above-mentioned cleaning, drying and pretreated flexible base, board are placed in the vacuum chamber, be evacuated to 1 * 10
-3Pa deposits organic function layer then on above-mentioned anode layer.Organic function layer comprises luminescent layer, can also comprise functional layers such as hole transmission layer, electron transfer layer.Luminescent layer can adopt small molecule material, also can adopt polymeric material.The luminescent layer material can be fluorescent material, as metal organic complex (as Alq
3, Gaq
3, Al (Saph-q) or Ga (Saph-q)) compounds, but dopant dye in this small molecule material, doping content is the 0.01wt%～20wt% of small molecule material, dyestuff is generally a kind of material in aromatic condensed ring class (as rubrene), Coumarins (as DMQA, C545T) or two pyrans class (as DCJTB, the DCM) compound, the luminescent layer material also can adopt phosphor material, wherein carbazole derivates such as CBP, polyvinylcarbazole (PVK) are material of main part, but Doping Phosphorus photoinitiator dye in this material of main part is as three (2-phenylpyridine) iridium (Ir (ppy)
3), two (2-phenylpyridine) (acetylacetone,2,4-pentanedione) iridium (Ir (ppy)
2(acac)), octaethylporphyrin platinum (PtOEP) etc.Hole transport layer material is generally the low molecular material of the arylamine class and the branch polymer same clan, as N, and N '-two-(1-naphthyl)-N, N '-diphenyl-1,1-xenyl-4,4-diamines (NPB), N, N '-diphenyl-N, N '-two (aminomethyl phenyl)-1,1 '-xenyl-4,4 '-diamines (TPD) etc.The electric transmission layer material is generally the micromolecule electron transport material, can be metal organic complex (as Alq
3, Gaq
3, Al (Saph-q), BAlq or Ga (Saph-q)), aromatic condensed ring class (as pentacene, perylene) or o-phenanthroline class (as Bphen, BCP) compound;
(4) preparation of negative electrode: keep above-mentioned vacuum chamber internal pressure constant, deposition cathode layer on above-mentioned organic function layer.Cathode layer generally adopts the alloy of the lower metal of work functions such as lithium, magnesium, calcium, strontium, aluminium, indium or they and copper, gold, silver, or the electrode layer that alternately forms of metal and metal fluoride;
(5) preparation of encapsulating structure: take out in the vacuum chamber and prepare the device that has finished, be sent to the preparation of carrying out encapsulated layer in the environment of the deoxygenation that dewaters by top step (1)-(4).
Hybrid desiccant equably in the polymeric material, the average-size of drier is 10nm～10 μ m, that its shape can be is granular, wire, spherical or sheet, the shared percent by volume of drier in polymer is about 10%～60%, and desiccant material is selected from alkaline-earth metal, alkaline earth oxide, zeolite, have in the metal alcoholate of long-chain hydrocarbon, at least a in the sulfate, halide, perchlorate.Preferable material comprises sodium, calcium, magnesium, barium, lithia, sodium oxide molybdena, potassium oxide, barium monoxide, calcium oxide, magnesium oxide, lithium sulfate, sodium sulphate, calcium sulfate, magnesium sulfate, sulfuric acid bores, gallium sulfate, titanium sulfate, nickelous sulfate, calcium chloride, magnesium chloride, cesium chloride, strontium chloride, beryllium chloride, yttrium chloride, copper chloride, gallium chloride, cesium fluoride, stannous fluoride, antimony fluoride, fluoridize tantalum, fluoridize niobium, lithium bromide, calcium bromide, comprise cerium bromide, selenium bromide, the bromination vanadium, magnesium bromide, barium iodide, magnesium iodide, at least a in barium perchlorate and the magnesium perchlorate.Polymeric material is preferably thermoset plastics, UV and solidifies a kind of in the glue etc.Be preferably a kind of in phenolic resins, Lauxite, melmac, unsaturated polyester resin, epoxy resin, organic siliconresin, polyurethane, polymethyl methacrylate, polyethyl methacrylate, the UV cured resin.
The preparation thick film layers: the polymeric material preparation that will be above-mentioned be mixed with drier is on the cathode layer of OLED device or prepare and all prepare in oled substrate emergent light one side or on the OLED cathode layer and in substrate emergent light one side, concrete preparation method comprises spin coating, inkjet printing, silk screen printing etc., make it to solidify by heating or ultraviolet light, be 1～10min curing time.The thickness of this thick film layers is 1～1000 μ m, and the area of thick film layers is greater than the luminous zone area of OLED device.
(6) can comprise stainless steel foil in the encapsulating structure of the present invention.
The preparation method who contains the stainless steel foil of titanium nitride layer: adopt the method for plasma enhanced chemical vapor deposition (PECVD) to prepare the stainless steel foil that contains titanium nitride layer.At background pressure is 1 * 10
-3Feed reactant gas silane and ammonia under the condition of Pa, and the flow of conditioned reaction, conditioned reaction chamber air pressure 5Pa～50Pa, reaction chamber temperature is below 50 ℃, with the power of the 10W～500W ceramic material of growing on stainless steel foil, growth time 10s～30min, thickness are 10nm～1000nm.In the environment of deoxygenation that dewaters, use ultra-violet curing glue to connect stainless steel foil and the device that contains titanium nitride, and use ultraviolet light polymerization, reach the purpose of air locking.
(7) can comprise the organic-inorganic alternate multi-layered film in the encapsulating structure of the present invention.
The preparation method of organic-inorganic alternate multiple encapsulating structure: aforementioned device is placed vacuum coating equipment, suction to 10
-4～10
-3Pa, unpolymerized polymer monomer layer in the back side of aforementioned device evaporation one deck liquid state makes its curing with ultraviolet irradiation, and irradiation time is 1～10min, liquid monomer layer becomes smooth solid film through the ultraviolet irradiation in-situ polymerization, and thickness is 50～1000nm; Utilizing the method or plasma enhanced chemical vapor deposition (hereinafter to be referred as the PECVD) method of magnetically controlled DC sputtering or rf magnetron sputtering to prepare ceramic material layer on above-mentioned polymer material layer, is 10 at background pressure
-4～10
-3Feed reacting gas under the Pa condition, the flow-rate ratio that the control reaction is got up, air pressure, system temperature and power and the reaction time of adjusting vacuum chamber, carry out the preparation of ceramic material layer, thickness is 10～1000nm; Repeat abovementioned steps, prepare the polymer material layer in 3 cycles and the thin layer that ceramic material layer replaces overlapping composition altogether; Adopt the knifing legal system to be equipped with the unpolymerized polymer monomer layer of one deck liquid state on the above-mentioned thin layer that replaces overlapping composition, become the smooth organic insulating material layer of one deck through ultraviolet irradiation 1～10min in-situ polymerization, thickness is 10～1000 μ m.
OLED/ thick film: desiccant particle
The device architecture schematic diagram as shown in Figure 1, wherein 1 is the substrate of OLED device, 2 is the anode of OLED device, 3 is the organic function layer of OLED device, 4 is the cathode layer of OLED device, 5 is the thick film layers in the OLED device encapsulation structure.
The device concrete structure:
Pet substrate/ITO/NPB/Alq
3/ Mg:Ag/ polymethyl methacrylate: CaO
(1) is carved with the cleaning of the pet substrate of ITO in advance: utilize alkali lye spray and the ultrasonic method of deionized water that transparent conduction base sheet is cleaned, place it in oven dry under the infrared lamp after the cleaning, ito glass to oven dry carries out the preliminary treatment that UV ozone is cleaned and the low energy oxygen ion beam bombards then, wherein the ITO film above the conductive substrate is as the anode layer of device, the square resistance of ITO film is 50 Ω, and thickness is 150nm;
(2) preparation of organic function layer: cleaning, drying and pretreated substrate place in the vacuum chamber, are evacuated to 1 * 10
-3Pa, evaporation one deck hole mobile material NPB on the ITO film then, evaporation speed is 0.5nm/s, thickness is 50nm; Evaporation one deck luminous organic material on hole mobile material, oxine aluminium Alq
3, evaporation speed is 0.5nm/s, thickness is 50nm;
(3) preparation of negative electrode: keep above-mentioned vacuum chamber internal pressure constant, on above-mentioned electron transfer layer successively evaporation MgAg alloy-layer as the cathode layer of device, thickness is 150nm, the Ag layer of evaporation 50nm again on the MgAg alloy-layer, and wherein alloy-layer prepares the method that adopts the double source evaporation;
(4) preparation of encapsulated layer: in polymethyl methacrylate, evenly mix granular CaO particle in advance, the average-size of CaO is that 100nm, volumetric concentration are 60%, adopt the mode of inkjet printing that this mixture is covered on the metallic cathode layer, the about 200 μ m of the thickness of encapsulated layer, the encapsulated layer area coverage is greater than the luminous zone area of device, to reach the purpose of air locking light-emitting zone.
OLED/ thick film/desiccant particle/thick film
The device concrete structure:
PES substrate/ITO/NPB/Alq
3/ Mg:Ag/ phenolic resins/sodium/UV glue
Step (1)～(3): preparation is with (1) (2) (3) of embodiment 1, and the substrate material of OLED device uses PES;
(4) preparation of encapsulated layer: take out the device that evaporation finishes in the vacuum chamber, be sent to the preparation of carrying out encapsulated layer in the environment of the deoxygenation that dewaters.At first the mode with knifing prepares one deck heat-curable glue phenolic resins on OLED device metal layer, the about 400 μ m of thickness, sprinkle spherical metal Na then, make it to become discontinuously arranged thereon, the about 10 μ m of the average-size of Na particle, then phenolic resins is heated to about 40 ℃, 10min makes it to solidify; Last spin coating UV glue (UV STRCTL 352, Le Tai company) uses the about 3min of ultraviolet lighting to make it to solidify the about 600 μ m of thickness on the surface of metal Na.The encapsulated layer area coverage is greater than the luminous zone area of device, thereby reaches the purpose of the light-emitting zone of air locking.
OLED/ thick film: desiccant particle/stainless steel paillon foil device
Structure as shown in Figure 2, wherein 1 is the substrate of OLED device, 2 is the anode of OLED device, 3 is the organic function layer of OLED device, 4 is the cathode layer of OLED device, 5 is the thick film layers in the OLED device encapsulation structure, 7 is the stainless steel paillon foil in the encapsulating structure.
The device concrete structure:
Aluminium foil/ITO/NPB/Alq
3/ Mg:Ag/ epoxyn: zeolite/the contain stainless steel foil of titanium nitride layer
(1)～(3): preparation is with (1) (2) (3) of embodiment 1, and just the substrate of OLED device uses aluminium foil;
(4) preparation of encapsulated layer:
Adopt the method for plasma enhanced chemical vapor deposition (PECVD) to prepare the stainless steel foil that contains titanium nitride layer.At background pressure is 1 * 10
-3Feed reactant gas silane and ammonia under the condition of Pa, and the flow of conditioned reaction, conditioned reaction chamber air pressure 40Pa, reaction chamber temperature is below 50 ℃, with the power of the 400W ceramic material of growing on stainless steel foil, growth time 10min, thickness is 800nm, prepares stainless steel foil.
The zeolite that in the epoxy resin adhesive, evenly mixes sheet, the average area of zeolite is that 200nm, volumetric concentration are 30%, adopt the mode of spin coating that this mixture is covered on the metallic cathode layer, the about 10 μ m of the thickness of thick film layers, the thick film layers area coverage is greater than the luminous zone area of device, to reach the purpose of air locking light-emitting zone.
The stainless steel foil that has prepared is connected with device, and pressurization makes it to solidify and connects, and the area of whole encapsulation layer structure reaches the purpose of the light-emitting zone of air locking greater than the effective area of device.
Thick film: desiccant particle/OLED/ thick film: desiccant particle
The device architecture schematic diagram as shown in Figure 3, wherein 1 is the substrate of OLED device, 2 is the anode of OLED device, 3 is the organic function layer of OLED device, 4 is the cathode layer of OLED device, 5 is the thick film layers in the encapsulating structure on the OLED device cathodes layer, and 6 is the thick film layers in the encapsulating structure of OLED device substrate one side.
The device concrete structure:
Polyethyl methacrylate: CaCl
2/ Polyimide substrate/ITO/NPB/Alq
3/ Mg:Ag/ Lauxite: MgSO
4
Step (1)～(3): preparation is with (1) (2) (3) of embodiment 1, and the OLED device substrate adopts polyimides;
(4) modification of substrate: even mixed C aCl in polyethyl methacrylate in advance
2Particle, CaCl
2Average grain diameter be that 10nm, volumetric concentration are 10%; Place mode that the environment of the deoxygenation that dewaters adopts knifing that aforementioned mixture is covered the relative side of Polyimide substrate ITO film cleaning, drying and pretreated ito substrate, solidify the about 1 μ m of back thickness, area is greater than the luminous zone area of device.
(5) preparation of encapsulated layer: in Lauxite, evenly mix MgSO in advance
4, MgSO
4Average-size be that 800nm, concentration are 40%, adopt the mode of silk screen printing that this mixture is covered on the metallic cathode layer, solidify the about 700 μ m of thickness of back encapsulated layer, the area of encapsulated layer reaches the purpose of air locking light-emitting zone greater than the luminous zone area of device.
Thick film: desiccant particle/OLED/ thick film: desiccant particle/stainless steel paillon foil
Polyurethane: CsF/PS substrate/ITO/NPB/Alq
3/ Mg:Ag/UV solidifies glue: Ba (ClO
4)
2/ contain the stainless steel foil of titanium nitride layer
Step (1)～(3): preparation is with (1) (2) (3) of embodiment 1, and the baseplate material of OLED device adopts PS;
(4) modification of substrate: even mixed C sF particle in polyurethane in advance, the average grain diameter of CsF is that 20nm, volumetric concentration are 20%; Place mode that the environment of the deoxygenation that dewaters adopts knifing that aforementioned mixture is covered the relative side of PS substrate ITO film cleaning, drying and pretreated ito substrate, solidify the about 10 μ m of back thickness, area is not less than the effective area of device.
(5) preparation of encapsulating structure: evenly mixing average grain diameter in UV curing glue is that 1 μ m, volumetric concentration are 50% Ba (ClO
4)
2Particle.Take out the device that evaporation finishes in the vacuum chamber, be sent to the preparation of carrying out encapsulated layer in the environment of the deoxygenation that dewaters.Adopt the PECVD method to prepare the stainless steel foil that contains titanium nitride layer.At background pressure is 1 * 10
-3Feed reactant gas silane and ammonia under the condition of Pa, and the flow of conditioned reaction, conditioned reaction chamber air pressure 10Pa, reaction chamber temperature be below 50 ℃, and with the power of the 100W ceramic material of growing on stainless steel foil, growth time 3min, thickness are 50nm.At first spin coating one deck contains Ba (ClO on OLED device metal layer
4)
2The UV of particle solidifies glue, and is connected with stainless steel foil, and ultraviolet lighting 5min makes it to solidify and connects the about 900 μ m of thickness.The area of whole encapsulated layer reaches the purpose of air locking light-emitting zone greater than the luminous zone area of device.
OLED/ organic-inorganic alternate multiple film/thick film: desiccant particle
The device concrete structure:
Ultra-thin glass/ITO/NPB/Alq
3/ Mg:Ag/ (UV glue/TiN)
3/ UV glue/organic siliconresin: SeBr
2
Step (1)～(3): preparation is with (1) (2) (3) of embodiment 1, and the substrate of OLED device uses ultra-thin glass;
(4) preparation of organic-inorganic alternate multiple film: OLEDs places vacuum coating equipment, is evacuated to 5 * 10
-4Pa.UV in the back side of device evaporation one deck liquid state solidifies glue (UV STRCTL 352, Le Tai company), makes its curing with ultraviolet irradiation, and irradiation time is 5min, and UV solidifies glue and becomes smooth solid film through the ultraviolet irradiation in-situ polymerization, and thickness is 300nm.At background pressure is 10
-4～10
-3Feed nitrogen under the Pa condition, the air pressure of regulating vacuum chamber is 0.40Pa, adopts the high purity titanium target solidifying sputter on the glue to UV under the direct current power of 96W, and substrate temperature is controlled at below 40 ℃, and growth time is 10min, and the titanium nitride membrane thickness is 50nm.Repeat UV curing glue/titanium nitride compound film layer that above-mentioned steps prepares 2 cycles again.At last, feed inert nitrogen gas in glove box, the UV that adopts the knifing legal system to be equipped with one deck liquid state on above-mentioned thin layer solidifies glue, makes its polymerization with ultraviolet irradiation 5min, and thickness is 70 μ m.
(5) preparation of encapsulating structure: in organic siliconresin, evenly mix SeBr in advance
2, SeBr
2Average-size be that 400nm, concentration are 40%, adopt the mode of silk screen printing that this mixture is covered on the metallic cathode layer, solidify the about 500 μ m of thickness of back encapsulated layer, the area of encapsulated layer reaches the purpose of air locking light-emitting zone greater than the luminous zone area of device.
Comparative Examples 1
The device concrete structure:
Pet substrate/ITO/NPB/Alq
3/ Mg:Ag/UV glue+aluminium foil
Step (1)～(3): preparation is with (1) (2) (3) of embodiment 1;
(4) Feng Zhuan preparation: the device that will prepare takes out and places the environment of the deoxygenation that dewaters, and UV glue on the point presses aluminium foil then around device, makes it to solidify with the about 3min of UV-irradiation, reaches the purpose of exclusion of water oxygen encapsulation.
Because gas permeation rate checkout equipment commonly used can only detect 10
-2G/m
2The above transmitance of/day, encapsulation back transmitance are all at this below scope, so come the influence of number of detection cycles to encapsulation performance with the oxidation of active metal Ca:
The packaging effect of above-mentioned three embodiment and Comparative Examples sees the following form:
Encapsulating structure is: PET substrate/Ca/ encapsulated layer
50 ℃ of temperature, with the naked eye the time of Ca complete oxidation is observed under the environment of humidity 95%:
| Encapsulating structure | Ca complete oxidation time/h |
| Comparative Examples 1 | 305.4 |
| |
700.4 |
| |
744.7 |
| |
786.8 |
| |
767.4 |
| |
800.6 |
| |
805.2 |
Although describe the present invention in conjunction with the preferred embodiments, the present invention is not limited to the foregoing description and accompanying drawing, and encapsulated layer especially of the present invention can prepare in device cathodes one side, also can prepare the surface in entire device.Should be appreciated that those skilled in the art can carry out various modifications and improvement under the guiding of the present invention's design, claims have been summarized scope of the present invention.
Claims (11)
1, a kind of flexible organic electroluminescent device, comprise encapsulating structure, it is characterized in that, encapsulating structure is the thick film layers that is formed by polymeric material, and contain drier in this thick film layers, drier shared volume percent content in thick film layers is 10%～60%, and the thickness of thick film layers is 1 μ m～1000 μ m, drier is of a size of 10nm～10 μ m, and that drier is selected from is granular, the material of wire, spherical or sheet.
2, organic electroluminescence device according to claim 1 is characterized in that the drier in the thick film layers in the described encapsulating structure is selected from alkali metal, alkaline-earth metal, metal oxide, halide, sulfate, perchlorate, zeolite, has at least a in the metal alcoholate of long-chain hydrocarbon.
3, organic electroluminescence device according to claim 2 is characterized in that described drier is selected from sodium, calcium, magnesium, barium, lithia, sodium oxide molybdena, potassium oxide, barium monoxide, calcium oxide, magnesium oxide, lithium sulfate, sodium sulphate, calcium sulfate, magnesium sulfate, sulfuric acid bores, gallium sulfate, titanium sulfate, nickelous sulfate, calcium chloride, magnesium chloride, cesium chloride, strontium chloride, beryllium chloride, yttrium chloride, copper chloride, gallium chloride, cesium fluoride, stannous fluoride, antimony fluoride, fluoridize tantalum, fluoridize niobium, lithium bromide, calcium bromide, comprise cerium bromide, selenium bromide, the bromination vanadium, magnesium bromide, barium iodide, magnesium iodide, at least a in barium perchlorate and the magnesium perchlorate.
4, organic electroluminescence device according to claim 1, the polymeric material that it is characterized in that thick film layers in the described encapsulating structure are preferably thermoset plastics or UV and solidify a kind of in the glue.
5, organic electroluminescence device according to claim 4 is characterized in that described polymeric material is preferably phenolic resins, Lauxite, melmac, unsaturated polyester resin, epoxy resin, organic siliconresin, polyurethane, polymethyl methacrylate, polyethyl methacrylate, UV and solidifies a kind of in the glue.
6, organic electroluminescence device according to claim 1, the thickness that it is characterized in that thick film layers in the described encapsulating structure are 10 μ m～1000 μ m.
7, organic electroluminescence device according to claim 1 is characterized in that described encapsulating structure is positioned at the one or both sides of organic electroluminescence device.
8, organic electroluminescence device according to claim 1, the substrate that it is characterized in that described device is selected from plastics, tinsel or ultra-thin glass for flexible.
9, organic electroluminescence device according to claim 8 is characterized in that described flexible substrate is preferably a kind of in polyesters, the polyimides compounds.
10, organic electroluminescence device according to claim 1 is characterized in that also comprising in the described encapsulating structure stainless steel foil lamella.
11, organic electroluminescence device according to claim 1 is characterized in that also comprising in the described encapsulating structure alternate multi-layered film of organic inorganic compounding.
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| CNB200710105977XA CN100553013C (en) | 2006-12-29 | 2007-06-05 | A kind of organic electroluminescence device |
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| CN200610167358.9 | 2006-12-29 | ||
| CN 200610167358 CN1976088A (en) | 2006-12-29 | 2006-12-29 | Organic electro luminescent device |
| CNB200710105977XA CN100553013C (en) | 2006-12-29 | 2007-06-05 | A kind of organic electroluminescence device |
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| CN100553013C true CN100553013C (en) | 2009-10-21 |
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| CN102237319A (en) * | 2010-04-23 | 2011-11-09 | 三星半导体(中国)研究开发有限公司 | Package |
| CN102299123A (en) * | 2011-05-20 | 2011-12-28 | 电子科技大学 | Method for packaging photoelectronic device |
| CN103137886A (en) * | 2011-11-25 | 2013-06-05 | 海洋王照明科技股份有限公司 | Composite packaging structure and packaging method for organic light-emitting devices |
| CN102593371A (en) * | 2012-03-16 | 2012-07-18 | 四川长虹电器股份有限公司 | Packaging structure for organic light-emitting device (OLED) |
| CN102709492A (en) * | 2012-06-13 | 2012-10-03 | 信利半导体有限公司 | Flexible organic electroluminescence display (OELD) and manufacture method thereof |
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| CN104064684A (en) * | 2013-03-21 | 2014-09-24 | 海洋王照明科技股份有限公司 | Organic electroluminescent device |
| CN103230727B (en) * | 2013-04-22 | 2015-06-24 | 陕西科技大学 | Drying agent for organic light-emitting device and preparation method for same |
| EP3087623B1 (en) | 2013-12-26 | 2021-09-22 | Kateeva, Inc. | Thermal treatment of electronic devices |
| KR101813828B1 (en) * | 2014-01-21 | 2017-12-29 | 카티바, 인크. | Apparatus and techniques for electronic device encapsulation |
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| CN106935726A (en) * | 2017-02-28 | 2017-07-07 | 深圳市华星光电技术有限公司 | Organic electroluminescence display device and method of manufacturing same and preparation method thereof |
| CN107359273A (en) * | 2017-06-20 | 2017-11-17 | 合肥市惠科精密模具有限公司 | A kind of high intensity AMOLED encapsulating structures |
| CN109860413B (en) * | 2018-11-21 | 2021-06-08 | 信利半导体有限公司 | Flexible display panel, device and preparation method of flexible display panel |
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