CN101128074A - An organic EL part and its making method - Google Patents

An organic EL part and its making method Download PDF

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Publication number
CN101128074A
CN101128074A CNA2007101220418A CN200710122041A CN101128074A CN 101128074 A CN101128074 A CN 101128074A CN A2007101220418 A CNA2007101220418 A CN A2007101220418A CN 200710122041 A CN200710122041 A CN 200710122041A CN 101128074 A CN101128074 A CN 101128074A
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layer
organic electroluminescence
electroluminescence device
organic
substrate
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张德强
刘嵩
邱勇
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
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Priority to CNA2007101220418A priority Critical patent/CN101128074A/en
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Abstract

The utility model relates to an encapsulation and preparation method of organic light emitting diode organic light emitting diode comprises an encapsulation structure, and the encapsulation comprises a pre-encapsulated layer and foil encapsulation sheets of moisture layers on the internal surface. The utility model has the advantages that the service life is prolonged in particular to soft screen; the manufacturing process is simplified; the production cost is reduced; and the bending property of screen body can be effectively ensured.

Description

A kind of organic electroluminescence device and preparation method thereof
Technical field
The present invention relates to encapsulating structure of a kind of organic electroluminescence 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.Newly occurred three kinds of Display Techniques in recent years: plasma display, Field Emission Display and display of organic electroluminescence (hereinafter to be referred as OLED) have all remedied the deficiency of cathode ray tube and LCD to a certain extent.Wherein, a series of advantages such as display of organic electroluminescence has from main light emission, low-voltage DC driven, solidifies entirely, the visual angle is wide, color is abundant, compare with LCD, display of organic electroluminescence does not need backlight, the visual angle is big, power is low, and its response speed can reach 1000 times of LCD, and its manufacturing cost but is lower than the LCD of equal resolution.Therefore, display of organic electroluminescence has broad application prospects, and is counted as the utmost point and composes one of following flat panel display of competitiveness.
The OLED product is technical from volume production, also do not reach at present the requirement of commercialization, realize the difficulty that the OLED volume production is faced, mainly contain the following aspects: the life problems of (1) OLED, (2) production technology and quality management problem, (3) correlation technique problem (particularly Driving technique), wherein, the life-span is one of greatest problem that faces at present.We can say that the life problems of OLED 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 OLED 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 OLED to lose efficacy, and are easy to and steam, oxygen reaction as the active metal of OLED 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 OLED 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% oxidized, the not light-emitting zone that forms is just very obviously (if the oxidation of negative electrode occurs in metal and at the interface organic, even only being 5 , ruined negative electrode 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 OLED requires should be less than 10 -5G/m 2/ day (Burrows PE, Graff GL, Gross ME, et al.Displays 22,652001).
Existing OLED method for packing is a helmet formula encapsulating structure, promptly uses metal or glass as cap, and adhesive is bonded together relative sealed space of formation at the edge that is coated on cap with cap and display screen; In order further to absorb steam, also need cap is made a groove, and xeraphium or drying sheet are filled in the groove of cap.This kind method for packing can well solve the injury to the OLED device of water, oxygen, but because entire display screen is to be made by two blocks of thick and heavy glass or metal, makes OLED lose its frivolous advantage; In addition, owing to have a groove on the cap, the center of cap certainly exists collapse-deformation, when the large-sized display screen of preparation, thisly subsides more obviously, and the pixel of the center of cap even the display screen that can rub is destroyed display screen; Because the variation of the gas pressure intensity in the groove produces a pressure difference with atmosphere, and then causes packaging plastic the crack to occur, destroy packaging effect in the process of subsiding.Simultaneously, the method for packing of at present this OLEDs based on glass substrate can't be applied to soft field of display, because soft screen device is when bending, and the bonding case chip destruction metal level that might rub.Nowadays, OLED 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.
Be directed to above situation, thin-film package technology progressively development and perfect, its representative is the compound thin-film package technology of the organic-inorganic of Vitex company.The characteristics of its technology are at first to utilize organic material to form a smooth plane in the device back side, the inorganic thin film that then forms a densification on this plane is to reach the ability that intercepts water, oxygen, because single inorganic thin film layer can't obtain good barriering effect, encapsulated layer need be prepared into the structure that multilayer replaces.But the organic polymer and the inorganic ceramic class material that prepare a plurality of cycles, 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 the organic layer or the metal electrode of OLED device 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.Therefore, this technology exists preparation section, equipment complexity in production application, and technology difficulty increases, and rhythm of production is slow, shortcomings such as the cost height of preparation.
Summary of the invention
Emphasis of the present invention proposes a kind of new encapsulating structure and method for packing at the problem that exists in the above-mentioned encapsulation technology, is particularly useful for flexible OLED.
The present invention proposes a kind of organic electroluminescence device, comprises substrate, anode, negative electrode and the organic function layer between two electrodes, also comprises encapsulating structure, comprises in this encapsulating structure: pre-packaged layer, inner surface preparation have the metal forming case chip of moisture absorption layer.
The material of pre-packaged layer is selected from a kind of in organic material, inorganic insulating material, the ceramic material, or being selected from the wherein composite material of the laminated construction of different materials formation, preferred material comprises AlQ, NPB, polyimides, epoxy resin, acrylic resin, polytetrafluoroethylene, SiO, SiO2, Si3N4, Al2O3, AlN, LiF, AlQ/LiF, SiO2/ epoxide-resin glue/SiO2, Al2O3/Alq3/Al2O3.
Can be mixed with hygroscopic material in the pre-packaged layer, this hygroscopic material is selected from calcium, calcium oxide, lithium nitride etc.
Metal foil material as case chip is selected from stainless steel foil, aluminium foil.The moisture absorption layer material of metal forming inner surface is selected from CaO, SrO, molecular sieve desiccant.
Outer surface at the metal forming case chip in the encapsulating structure can also have the one layer of polymeric material.
The substrate of device of the present invention can be flexibility, and its material is selected from plastics or ultra-thin glass.
Technical scheme advantage of the present invention: be improved the device lifetime after the encapsulation, when particularly being applied to soft screen, can increase substantially the life-span of prepared device, simplifies preparation technology, reduces production costs, and effectively guaranteed the bending performance of screen body simultaneously.
Description of drawings
Fig. 1 is the encapsulating structure schematic diagram of device in the embodiments of the invention, and wherein 1 is that substrate, 2 is that anode, 3 is that hole transmission layer, 4 is that luminescent layer, 5 is that electron transfer layer, 6 is that moisture absorption layer, 9 is that tinsel, 10 is adhesive linkage for negative electrode, 7 is pre-packaged layer, 8;
Fig. 2 is the brightness decay curve of device among the embodiment 3 among the present invention.
Embodiment
(1) preparation method of organic luminescent device OLED:
On substrate, prepare anode, organic function layer and negative electrode successively:
The substrate transparent substrate can be glass or flexible substrate, and flexible substrate adopts a kind of material in polyesters, polyimides compounds, tinsel or the ultra-thin glass;
Anode layer can adopt inorganic material or organic conductive polymer, inorganic material is generally the higher metals of work function such as metal oxides such as ITO, zinc oxide, zinc tin oxide or gold, copper, silver, the optimized ITO that is chosen as, organic conductive polymer are preferably a kind of material in polythiophene/polyvinylbenzenesulfonic acid sodium (hereinafter to be referred as PEDOT:PSS), the polyaniline (hereinafter to be referred as PANI);
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, the present invention is preferably Mg:Ag alloy-layer, Ag layer and LiF layer successively, Al layer successively;
Organic function layer comprises luminescent layer, can also comprise functional layers such as electron transfer layer, hole transmission 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, can be doped with dyestuff 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.
Electron transfer layer, materials used are 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.
Hole transmission layer, the material that uses is generally the low molecular material of the arylamine class and the branch polymer same clan, as N, 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.
Concrete preparation method at first cleans the substrate that is carved with anode in advance, evaporation hole transport layer material, luminescent layer material and electric transmission layer material successively thereon then, and the method by evaporation prepares cathode layer at last.
(2) preparation method of the organic light-emitting device encapsulating structure of the present invention's proposition:
At first on the device cathodes layer, prepare pre-packaged layer:
Pre-packaged layer can be a kind of in organic material (as Alq3, NPB, polyimides, ultra-violet curing glue, organic silica gel, fluoropolymer) and the inorganic insulating material (as LiF, SiO, SiO2, SiNx, SiOxNy, Al2O3), or is selected from wherein different materials formation laminated construction.When being prepared into laminated construction, can in lamination, add moisture absorption layer, make the Al2O3/Alq3/Ca/Alq3/Al2O3 structure that hygroscopic material prepares, or available Li3N makes the Teflon/Li3N/Teflon/Li3N/Teflon structure of hygroscopic material preparation as available Ca.
Concrete preparation method can be hot vapour deposition method, electron beam evaporation plating, sputter, vapour deposition, spin coating, printing.
Prepare the metal forming case chip then:
Can be earlier with the preparation of hygroscopic materials such as CaO, SrO on the polymer of softness (as PET etc.) substrate, be made into drying sheet, stick on the tinsel with epoxide-resin glue; Also hygroscopic materials such as CaO, SrO can be blended in epoxide-resin glue, the acrylic compounds colloid, pass through UV illumination or add hot preparation on tinsel; Also liquid driers such as molecular sieve can be prepared on tinsel with methods such as spin coating, printings, through adding the thermosetting moisture absorption layer.
On the tinsel for preparing, do not have local epoxy resin coating glue, the acrylic compounds colloid of moisture absorption layer, can use the tinsel that carries bonding agent yet, tinsel is pasted on the device with moisture absorption layer.
Can prepare one layer of polymeric (solidifying materials such as glue) with methods such as spin coating, printings at the tinsel back side as polyimides, polyester, UV.
Embodiment 1
(1) on substrate, prepare anode, organic function layer and negative electrode:
(1-1) be carved with the cleaning of ito glass substrate in advance: utilize the ultrasonic and ultrasonic method of deionized water of the washing agent of heat that the transparent conduction base sheet ito glass is cleaned, place it in oven dry under the infrared lamp after the cleaning, ito substrate 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; (1-2) preparation of organic luminous layer: place in the vacuum chamber with above-mentioned cleaning, drying and through pretreated ito glass, be evacuated to 1 * 10 -3Pa, evaporation one deck hole mobile material NPB on above-mentioned ITO film then, the evaporation speed of material film is 0.5nm/s, thickness is 50nm; Evaporation one deck luminous organic material on hole mobile material, oxine aluminium Alq, the evaporation speed of material film is 0.5nm/s, thickness is 50nm;
(1-3) preparation of negative electrode: keep above-mentioned vacuum chamber internal pressure constant, evaporation MgAg alloy-layer is as the cathode layer of device successively on above-mentioned electron transfer layer, and thickness is 8nm.The Ag layer of evaporation 15nm again on the MgAg alloy-layer.Wherein alloy-layer adopts the method for double source evaporation to mix;
(2) encapsulating structure of fabricate devices:
(2-1) preparation of pre-packaged layer: keep the interior pressure of above-mentioned vacuum cavity constant, evaporation polymeric material polyimides on above-mentioned cathode layer, thickness is 200nm.
(2-2) preparation of moisture absorption layer on the metal forming case chip: the stainless steel paillon foil is tiled on the smooth glass plate, the ultra-violet curing glue that is mixed with the CaO of 50% weight ratio prepares on the stainless steel paillon foil with printing process, the film thickness of preparation is 50 μ m, and the UV rayed makes UV glue film hardening.
(2-3) tinsel is pasted: solidify glue with UV and connect stainless steel paillon foil and device substrate, solidify through the UV rayed.
Embodiment 2
(1) method according to embodiment 1 prepares anode, organic function layer and negative electrode on glass substrate.
(2) encapsulating structure of fabricate devices:
(2-1) preparation of pre-packaged layer: keep the interior pressure of above-mentioned vacuum cavity constant, evaporation organic material Alq3 on above-mentioned cathode layer, evaporation rate is 0.5nm/s, thickness is 100nm; Evaporation inorganic material SiO on organic material Alq3, evaporation rate is 0.5nm/s, thickness is 200nm.
(2-2) preparation of moisture absorption layer on the metal forming case chip: aluminium foil is tiled on the smooth glass plate, is sent in the nitrogen environment, the Al2O3 molecular sieve desiccant is prepared on aluminium foil with printing process, 170 ℃ of bakings form moisture absorption layer through high temperature.
(2-3) tinsel is pasted: solidify glue with UV and connect aluminium foil and device substrate, solidify through the UV rayed.
Embodiment 3
(1) method according to embodiment 1 prepares anode, organic function layer and negative electrode on substrate, and just the material with substrate is changed to plastics.
(2) encapsulating structure of fabricate devices:
(2-1) keep the interior vacuum degree of above-mentioned vacuum cavity constant, the Alq3/LiF structure in four cycles of evaporation on cathode layer.The evaporation speed of Alq3 film is 0.5nm/s, and thickness is 80nm; The evaporation speed of LiF film is 0.2nm/s, and thickness is 20nm.
(2-2) the CaO drying sheet is sticked on the aluminium foil that is coated with epoxide-resin glue.
(2-3) aluminium foil that will be pasted with drying sheet pastes on the substrate.
Embodiment 4
(1) method according to embodiment 1 prepares anode, organic function layer and negative electrode on substrate, and just the material with substrate is changed to plastics.
(2) encapsulating structure of fabricate devices:
(2-1) keep the interior vacuum degree of above-mentioned vacuum cavity constant, with the method depositing Al 2O3 film of sputter, the speed of deposition is 0.3nm/s on cathode layer, and the thickness of deposition is 100nm.
(2-2) the SrO drying sheet is sticked on the aluminium foil that is coated with acrylate glue.
(2-3) aluminium foil that will be pasted with drying sheet pastes on the substrate.
Embodiment 5
(1) method according to embodiment 1 prepares anode, organic function layer and negative electrode on substrate, and just the material with substrate is changed to plastics.
(2) encapsulating structure of fabricate devices:
(2-1) keep the interior vacuum degree of above-mentioned vacuum cavity constant, evaporating Al 2O3 on cathode layer, deposition rate is 0.5nm/s, thickness is 80nm; Evaporating Al q3 on Al2O3, deposition rate is 0.5nm/s, thickness is 40nm; Evaporation active metal Ca on Alq3, deposition rate is 1nm/s, thickness is 50nm; Repeat the deposition process of Alq3 and Al2O3, prepare the Alq3 of 40nm/s and the Al2O3 of 80nm successively.
(2-2) the CaO drying sheet is sticked on the aluminium foil that is coated with acrylate glue.
(2-3) aluminium foil that will be pasted with drying sheet pastes on the substrate.
Embodiment 6
(1) method according to embodiment 1 prepares anode, organic function layer and negative electrode on substrate, and just the material with substrate is changed to plastics.
(2) encapsulating structure of fabricate devices:
(2-1) keep the pressure of above-mentioned vacuum cavity constant, sputter SiO2 on negative electrode, deposition rate is 0.5nm/s, thickness is 100nm; Epoxy resin evaporation ultra-violet curing glue on SiO2, the thickness of film is 100nm, solidifies through the UV rayed; Solidify sputter SiO2 on the glue at UV, deposition rate is 0.5nm/s, thickness 40nm.
(2-2) the acrylic compounds UV that deposits 100 μ m with printing process on aluminium foil solidifies glue, solidifies through the UV rayed; Another side at aluminium is coated with Al2O3 molecular sieve liquid drier with spin-coating method, and the back that is heating and curing forms moisture absorption layer, and thickness is 20 μ m.
(2-3) prolong aluminium foil edge coating UV and solidify glue, paste on the substrate, UV shines curing.
Comparative Examples 1
Method according to embodiment 1 prepares anode, organic function layer and negative electrode on substrate.Device does not encapsulate.
Comparative Examples 2
Method according to embodiment 1 prepares anode, organic function layer and negative electrode on substrate, just the material with substrate is changed to plastics.Device does not encapsulate.
The device of the foregoing description and Comparative Examples is under the brightness at the beginning of 2000cd/m2, and the time that brightness partly declines is:
Device Brightness partly decline the time (hrs)
Comparative Examples 1 25
Embodiment 1 2422
Embodiment 2 3156
Comparative Examples 2 12
Embodiment 3 996
Embodiment 4 852
Embodiment 5 1009
Embodiment 6 728
As seen, above-mentioned encapsulation technology can effectively improve the life-span of OLED device.
Although describe the present invention in conjunction with the preferred embodiments, the present invention is not limited to the foregoing description, 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 (9)

1. organic electroluminescence device, comprise substrate, anode, negative electrode and the organic function layer between two electrodes, also comprise encapsulating structure, it is characterized in that, comprise in this encapsulating structure: pre-packaged layer and inner surface preparation have the metal forming case chip of moisture absorption layer.
2. organic electroluminescence device according to claim 1 is characterized in that, the material of described pre-packaged layer is selected from a kind of in organic material, inorganic insulating material, the ceramic material, or is selected from the composite material of the laminated construction that different materials wherein forms.
3. organic electroluminescence device according to claim 2, it is characterized in that the material of described pre-packaged layer is preferably from AlQ, NPB, polyimides, epoxy resin, acrylic resin, polytetrafluoroethylene, SiO, SiO2, Si3N4, Al2O3, AlN, LiF, AlQ/LiF, SiO2/ epoxide-resin glue/SiO2, Al2O3/Alq3/Al2O3.
4. organic electroluminescence device according to claim 1 is characterized in that, is mixed with hygroscopic material in the described pre-packaged layer.
5. organic electroluminescence device according to claim 4 is characterized in that, the hygroscopic material in the described pre-packaged layer is selected from calcium, calcium oxide or lithium nitride.
6. organic electroluminescence device according to claim 1 is characterized in that, described metal foil material as case chip is selected from stainless steel foil, aluminium foil.
7. organic electroluminescence device according to claim 1 is characterized in that, the moisture absorption layer material of described metal forming inner surface is selected from CaO, SrO, molecular sieve desiccant.
8. organic electroluminescence device according to claim 1 is characterized in that, the outer surface at the metal forming case chip in the encapsulating structure has the one layer of polymeric material.
9. organic electroluminescence device according to claim 1, the substrate that it is characterized in that described device is for flexible, and its material is selected from plastics or ultra-thin glass.
CNA2007101220418A 2007-09-20 2007-09-20 An organic EL part and its making method Pending CN101128074A (en)

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