CN1832222A - Organic electroluminescent device and manufacturing method for the same - Google Patents

Organic electroluminescent device and manufacturing method for the same Download PDF

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Publication number
CN1832222A
CN1832222A CNA2005101217115A CN200510121711A CN1832222A CN 1832222 A CN1832222 A CN 1832222A CN A2005101217115 A CNA2005101217115 A CN A2005101217115A CN 200510121711 A CN200510121711 A CN 200510121711A CN 1832222 A CN1832222 A CN 1832222A
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Prior art keywords
electroluminescence device
organic electroluminescence
organic
moisture absorption
absorption layer
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CNA2005101217115A
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CN1832222B (en
Inventor
赵尹衡
李钟赫
李海承
金元钟
崔镇白
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Samsung Display Co Ltd
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Samsung SDI Co Ltd
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Priority claimed from KR1020040090492A external-priority patent/KR100669751B1/en
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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
    • H10K50/846—Passivation; Containers; Encapsulations comprising getter material or desiccants
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

An organic electroluminescent device includes a substrate, an encapsulation substrate, an organic electroluminescent portion interposed between the substrate and the encapsulation substrate and a transparent moisture absorption layer. The transparent moisture absorption layer comprises at least one of a metal oxide and a metal salt with an average particle diameter of about 100 nm or less, a binder, and a dispersant. The transparent moisture absorption layer may be disposed in an internal space provided by the substrate and the encapsulation substrate and may be used in a front emission type organic electroluminescent device.

Description

Organic electroluminescence device and manufacture method thereof
The cross reference of associated documents
The application requires the Korean Patent Application No. 10-2004-0090491 that submits in Korea S Department of Intellectual Property on November 8th, 2004 and priority and the rights and interests of 10-2004-0090492, the whole contents of these files this in conjunction with and as a reference.
Background of invention
Invention field
The present invention relates to a kind of organic electroluminescence device that comprises transparent moisture absorption layer, this transparent moisture absorption layer can be used for positive emissive devices, and a kind of method of making this organic electroluminescence device.
Background technology
Because the infiltration of moisture, organic electroluminescence device are easy to damage.Therefore, need hermetically-sealed construction to guarantee the stable driving and the long term life of organic electroluminescence device.
Usually, metal shell or the glass substrate that forms the lid with groove is used for organic electroluminescence device.For moisture absorption, the drier powder is arranged in the groove or desciccator diaphragm adheres on the groove with bilateral band shape.
Japanese patent application publication No. JP 9-148066 discloses a kind of organic electroluminescence device that comprises duplexer, and wherein this duplexer has a pair of electrode that faces with each other, and the luminous organic material that is made of organic compound is placed between these electrodes.This device also comprises and prevents that this duplexer is exposed to airborne gas-tight container and is configured in the drying device that is made of for example alkali metal oxide in the gas-tight container.Yet the macrostructure of gas-tight container has increased the gross thickness of organic electroluminescence device.Equally, the opacity of drying device causes the manufacturing of positive surface emitting type organic electroluminescence device to become difficult, although drying device still keeps solid-state after absorbing moisture.
U.S. Pat 6226890 discloses a kind of organic electroluminescence device that comprises the moisture absorption layer that utilizes drier and adhesive manufacturing.This moisture absorption layer comprises the solid particle that particle diameter is 0.1-200 μ m.
Yet organic electroluminescence device is translucent or opaque, thereby can not be used as positive emissive devices, and has lower wettability power.
Summary of the invention
The invention provides a kind of organic electroluminescence device that comprises transparent moisture absorption layer, this transparent moisture absorption layer has good wettability power and can be used for positive emissive devices, and a kind of method of making this organic electroluminescence device is provided.
The present invention also provides a kind of preparation to be used to form the method for compositions of transparent moisture absorption layer, this layer has good wettability power and can be used for positive emissive devices, and a kind of organic electroluminescence device that comprises the transparent moisture absorption layer of the composition formation that utilizes this method preparation is provided.
Other features of the present invention will propose in the following description, and part is apparent from describe, and perhaps can understand by enforcement of the present invention.
The invention discloses a kind of organic electroluminescence device, comprise substrate, seal substrate places organic electroluminescent part and transparent moisture absorption layer between substrate and the seal substrate.Transparent moisture absorption layer comprises that average grain diameter is at least a in about 100nm or littler metal oxide and the slaine, adhesive and dispersant.Transparent moisture absorption layer is configured in the inner space that is provided by substrate and seal substrate.
The invention also discloses a kind of organic electroluminescence device, comprise substrate, seal substrate, place organic electroluminescent part and transparent moisture absorption layer between substrate and the seal substrate.Transparent moisture absorption layer comprises at least a in metal oxide and the slaine, and it is in the particle grain size that accounts for 10% weight (D10) and account for and have 100nm or littler difference between the particle grain size (D90) of 90% weight and be configured in the inner space that is provided by substrate and seal substrate.
The invention also discloses a kind of organic electroluminescence device, comprise substrate, seal substrate places the organic electroluminescent part between substrate and the seal substrate and the transparent moisture absorption layer of the inner space that is provided by substrate and seal substrate is provided.Transparent moisture absorption layer comprises that average grain diameter is at least a in about 100nm or littler metal oxide and the slaine, and adhesive.The thickness of transparent moisture absorption layer is that about 100 μ m are to about 300 μ m.Transparent moisture absorption layer has about 95% or bigger transmissivity.
The invention also discloses a kind of method that is used to make organic electroluminescence device, comprise forming and comprise first electrode that is layered on the substrate, organic layer, organic electroluminescent part with second electrode, coating is used to form the composition of transparent moisture absorption layer in the inner space that is provided by substrate and seal substrate, solidify said composition to obtain transparent moisture absorption layer, in substrate and seal substrate one of at least on the exterior domain place sealant of organic electroluminescent part, and connect substrate and seal substrate.The composition that is used to form transparent moisture absorption layer comprises that average grain diameter is at least a in about 100nm or littler metal oxide and the slaine, adhesive, dispersant and solvent.
The invention also discloses a kind of method that is used to make organic electroluminescence device, comprise forming and comprise first electrode of sequential cascade on substrate, organic layer, organic electroluminescent part with second electrode, coating is used to form the composition of transparent moisture absorption layer in the inner space that is provided by substrate and seal substrate, solidify said composition to obtain transparent moisture absorption layer, in substrate and seal substrate one of at least on the exterior domain place sealant of organic electroluminescent part, and connect substrate and seal substrate.The composition that is used to form transparent moisture absorption layer comprises at least a in metal oxide and the slaine, and it is in the particle grain size that accounts for 10% weight (D10) and account between the particle grain size (D90) of 90% weight and have 100nm or littler difference, and solvent.
The invention also discloses a kind of preparation and be formed with the method for compositions of the transparent moisture absorption layer of organic electroluminescence devices, comprise at least a and solvent in metal oxide and the slaine to obtain dispersion and to grind this dispersion.
Should be appreciated that the general introduction of front and detailed description hereinafter are exemplary and indicative, and as claim, plan to provide further explanation of the present invention.
Description of drawings
Appended accompanying drawing is used to provide further understanding of the present invention, and in conjunction with in this application, constitutes the application's a part, these description of drawings embodiment of the present invention, and with describe one and be used from and explain principle of the present invention.
Figure 1A, 1B, 1C and 1D are the schematic section according to the organic electroluminescence device of illustrative embodiments of the invention.
Fig. 2 A is scanning electron microscopy (SEM) photo that the cross section of the transparent moisture absorption layer that obtains in embodiment 1 has been described.
Fig. 2 B is the SEM photo that the cross section of the transparent moisture absorption layer that obtains in embodiment 6 has been described.
Fig. 3 has illustrated the transmitted spectrum of the transparent moisture absorption layer that obtains in embodiment 1.
Fig. 4 is the curve chart of the moisture absorption of the transparent moisture absorption layer that obtains in embodiment 1, embodiment 8 and Comparative Examples 5.
Fig. 5 A shows the image of the organic electroluminescence device that obtains in embodiment 1, Comparative Examples 1 and Comparative Examples 2.
Fig. 5 B has illustrated the life-span of the organic electroluminescence device that obtains in embodiment 8 and Comparative Examples 5.
Fig. 6 has illustrated the transmitted spectrum of the transparent moisture absorption layer that obtains in embodiment 6, embodiment 7, Comparative Examples 6 and Comparative Examples 7.
Fig. 7 and Fig. 8 are respectively the curve charts of the particle size distribution of CaO in the composition that is used to form transparent moisture absorption layer that obtains in according to the embodiment 14 of illustrative embodiments of the invention and embodiment 20.
The detailed description of specific embodiments
Below, will the present invention more fully be described with reference to appended accompanying drawing, wherein embodiment of the present invention are shown in the drawings.Yet the present invention can specialize and should not be defined as embodiment described herein with many different forms.Certainly, provide these embodiments, and will pass on scope of the present invention fully for those skilled in the art so that this specification is detailed.In the accompanying drawings, the size in layer and zone and relative size are amplified in order to know.
Should be appreciated that can directly can there be insertion element in it on another element or also when element when for example layer, film, zone or substrate are called as on another element.On the contrary, when element is called as directly on another element, there is not insertion element to exist.
The invention provides a kind of organic electroluminescence device with long life, it can utilize transparent moisture absorption layer to make, and this layer has fabulous moisture and the oxygen absorption characteristic and the high grade of transparency with respect to conventional getter.In this organic electroluminescence device, can be used as frontside substrate through the glass substrate of over etching or the flat glass that is not etched.Thereby, because the structural disadvantages that the use of etching glass substrate causes can overcome.
In addition, because the composition that is used to form transparent moisture absorption layer prepared in accordance with the present invention comprises the metal oxide particle of nano-scale, for example be dispersed in wherein calcium oxide particle, so scattering can not take place in the moisture absorption layer that utilizes said composition to form with high concentration.Thereby moisture absorption layer is transparent.Transparent moisture absorption layer can be used for positive surface emitting type organic electroluminescence device.
Organic electroluminescence device comprises the transparent moisture absorption layer that is suitable for positive emissive devices according to embodiments of the present invention.Transparent moisture absorption layer forms by the composition that coating and curing are used to form transparent moisture absorption layer.Composition comprises that average grain diameter is 100nm or littler metal oxide and/or slaine, adhesive, dispersant and solvent.Metal oxide and water reaction are removed water thus to destroy metal-oxygen-metallic bond and to form metal hydroxides.Under the situation of slaine, the empty binding site coordination of hydrone and central metal to be forming stable compound, thereby removes water.
Metal oxide and slaine for example can comprise alkali metal oxide, alkaline earth oxide, metal halide, metal sulfate, metal perchlorate, or phosphorus pentoxide (P 2O 5).
Alkali metal oxide for example can comprise lithia (Li 2O), sodium oxide molybdena (Na 2Or potassium oxide (K O), 2O).Alkaline earth oxide for example can comprise barium monoxide (BaO), calcium oxide (CaO), or magnesium oxide (MgO).Metal sulfate for example can comprise lithium sulfate (Li 2SO 4), sodium sulphate (Na 2SO 4), calcium sulfate (CaSO 4), magnesium sulfate (MgSO 4), cobaltous sulfate (CoSO 4), gallium sulfate (Ga 2(SO 4) 3), titanium sulfate (Ti (SO 4) 2), or nickelous sulfate (NiSO 4).Metal halide for example can comprise calcium chloride (CaCl 2), magnesium chloride (MgCl 2), strontium chloride (SrCl 2), yttrium chloride (YCl 2), copper chloride (CuCl 2), cesium fluoride (CsF), tantalum pentafluoride (TaF 5), fluoridize niobium (NbF 5), lithium bromide (LiBr), calcium bromide (CaBr 3), comprise cerium bromide (CeBr 4), selenium bromide (SeBr 2), bromination vanadium (VBr 2), magnesium bromide (MgBr 2), barium iodide (BaI 2), or magnesium iodide (MgI 2).The metal perchlorate for example can comprise barium perchlorate (Ba (ClO 4) 2) or magnesium perchlorate (Mg (ClO 4) 2).
In embodiments of the invention, utilize physics and chemical method, so that it has about 100nm or littler average grain diameter with metal oxide or slaine fine grinding.
Metal oxide or slaine particle can have about 100nm or littler, are in particular the average grain diameter of about 50nm to about 90nm.If the average grain diameter of metal oxide or slaine particle is greater than 100nm, scattering may take place in visible-range in utilizing these granuloplastic moisture absorption layers, thereby causes fuzzy (dim phenomenon appears in layer) and reduce transmissivity.
Adhesive can be organic bond, inorganic bond, organic/inorganic composite adhesive, or its mixture.Organic bond can have low-molecular-weight or HMW.Organic bond should be compatible with metal oxide or slaine particle and be had fabulous ability with cambium layer.Organic bond can include but not limited to following substances: acrylic resin, methacrylic resin, polyisoprene, vinyl, epoxy resin, polyurethane resin, and celluosic resin.The example of acrylic resin can comprise butyl acrylate, acrylic acid ethylhexyl etc.The example of methacrylic resin can comprise propylene glycol methacrylate, tetrahydrofurfuryl methacrylate etc.The example of vinyl can comprise vinylacetate, N-vinyl pyrrolidone etc.The example of epoxy resin can comprise cycloaliphatic epoxides etc.The example of polyurethane resin can comprise urethane acrylate etc.The example of celluosic resin can comprise celluloid etc.
Inorganic bond can be metal or nonmetal, for example silicon, aluminium, titanium or zirconium.Inorganic bond can be compatible with metal oxide or slaine particle and be had fabulous ability with cambium layer.Inorganic bond can include but not limited to following substances: titanium dioxide, silica, zirconia, aluminium oxide and its precursor.
The organic/inorganic composite adhesive can comprise via the organic material that is covalently bound to metal or nonmetal for example silicon, aluminium, titanium or zirconium.The organic/inorganic composite adhesive should be compatible with metal oxide or slaine particle and be had fabulous ability with cambium layer.The organic/inorganic composite adhesive can include but not limited to following substances: epoxy silane or derivatives thereof, vinyl silanes or derivatives thereof, amine silane or derivatives thereof, methacrylate silanes or derivatives thereof and its partly solidified product.The physical characteristic that partly solidified product is used for the control combination thing is viscosity for example.
The object lesson of epoxy silane or derivatives thereof can comprise 3-glycidoxy-propyltrimethoxy silane and its polymer.
The vinyl silanes or derivatives thereof can comprise for example vinyltriethoxysilane and its polymer.
The object lesson of amine silane or derivatives thereof can comprise for example 3-aminopropyl triethoxysilane and its polymer.
The methacrylate silanes or derivatives thereof for example can comprise 3-(trimethoxysilyl) propyl acrylate and its polymer.
Be used for adhesive of the present invention and also can have fabulous thixotropy, it allows printing and fabulous levelling characteristic.
The concentration of adhesive can for about 10% weight to about 5000% weight, based on the weight meter of metal oxide and slaine.If the concentration of adhesive is less than 10% weight, then transparent moisture absorption layer can not easily form.If the concentration of adhesive is greater than 5000% weight, then wettability power descends.
When mixing with adhesive, the dispersant that is used for embodiment of the present invention can increase dispersibility in the drier dispersion.Dispersant can comprise HMW organic dispersing agent, HMW organic/inorganic composite dispersing agent, organic acid and inorganic acid, but is not limited to these materials.
Dispersant can comprise following at least a organic compound, but is not limited thereto: acrylic resin, methacrylic resin, polyurethane resin, polyisoprene, vinylite, epoxy resin, amide resin, sulphone resin, phthalic acid ester resin, phenolate resin and celluosic resin.Dispersant can also comprise following at least a metallic alkoxide compound, but is not limited thereto: silicon alkoxide (silicon alkoxide), titanium alkoxide, aluminium-alcohol salt, organic/inorganic comprehensive silicon alkoxide polymer, organic/inorganic composite titanium polymer and organic/inorganic clad aluminum alkoxide polymer.In addition, dispersant for example can comprise for example acetate of pentanedione and/or organic acid.
The instantiation of acrylic resin can comprise polyacrylate.The instantiation of methacrylic resin can comprise polymethacrylates.The instantiation of celluosic resin can comprise cellulose acetate.Organic compound can have the mean molecule quantity of 8000-15000.
The example of silicon alkoxide can comprise silester.The example of titanium alkoxide can comprise isopropyl titanate.The example of aluminium-alcohol salt can comprise aluminium butoxide.The example of organic/inorganic comprehensive silicon alkoxide polymer can comprise silicic acid glycidyl ester.The example of organic/inorganic composite titanium polymer can comprise titanium polymer (for example 2-Ethylhexyl Alcohol titanium).The example of organic/inorganic clad aluminum alkoxide polymer can comprise aluminium acetylacetonate.
When using dispersant, metal oxide particle in the transparent moisture absorption layer such as CaO can have nano level approximately diameter.If do not use dispersant, then metal oxide particle can be assembled in processing procedure, thereby can not exist with nanoscale in final transparent moisture absorption layer, even metal oxide particle has nano level particle diameter at first.
Can not assemble and precipitate for the fine particle in the dispersion soln, can use two kinds of methods.In first method, particle surface is charged by plus or minus, and owing to the electrostatic repulsion forces between the charged particle prevents to assemble.This allows particle easily to be dispersed in the solution and keeps the electrical characteristics of particle.Yet electric repulsive force may be subjected to the very big influence of pH value of solution value, so dispersibility reduces easily.
In the second approach, particle is centered on by high molecular weight dispersant, and this dispersant is owing to the steric hindrance between them has prevented gathering.In the method, can use wide region solvent and no matter their polarity, so that high dispersion stability to be provided.Yet the particle with electrical characteristics can be not used in this method, and the dispersant that uses is very expensive.The dispersant that is used for the drier dispersion of embodiment of the present invention has HMW, thereby when dispersant mixed with adhesive, dispersibility can keep and solution can evenly mix.
Form the dispersant in the composition of transparent moisture absorption layer concentration can for about 1% weight to about 100% weight, based on the weight meter of metal oxide and slaine.If the concentration of dispersant is less than 1% weight, then metal oxide may be dispersed in the composition unevenly.If the concentration of dispersant is greater than 100% weight, then the relative concentration of metal oxide can reduce unfriendly in the composition.
Solvent can also comprise polar solvent and non-polar solven.
The example of polar solvent can comprise alcohol, ketone etc., but is not limited thereto.The example of non-polar solven can comprise based on aromatic hydrocarbons, based on alicyclic with based on the organic solvent of aliphatic hydrocarbon.Solvent can comprise at least a in the following substances: ethanol, methyl alcohol, propyl alcohol, butanols, isopropyl alcohol, butanone, propylene glycol monomethyl ether (PGM), isopropyl cellulose (IPC), carrene, ethlyene dichloride, methyl cellosolve (MC) and ethyl cellosolve (EC).
In the composition concentration of solvent can for about 400% weight to about 1900% weight, based on the weight meter of metal oxide and slaine.If the concentration of solvent is less than about 400% weight, the effect that then adds solvent is too faint.If the concentration of solvent is greater than 1900% weight, then the relative concentration of metal oxide reduces unfriendly in the composition.
The thickness of transparent moisture absorption layer can utilize above-mentioned adhesive and dispersant to form.The amount of moisture that absorbs can increase by the concentration that increases the nano-scale drier, and wherein drier is infused in this layer.By the suitable type of selection adhesive, even thickness is that 100 μ m or bigger layer can be highly transparents.The viscosity that forms the composition of transparent moisture absorption layer also can be controlled by utilizing adhesive.Transparent moisture absorption layer can utilize printing process to form.
The transparent moisture absorption layer that is configured in the inner space that is provided by substrate and seal substrate can be provided organic electroluminescence device of the present invention.Particularly, transparent moisture absorption layer can be formed on the inner surface of the seal substrate shown in Figure 1A and Fig. 1 D, shown in Figure 1B, be formed on the sidewall of sealant layer, or be formed on the part one of at least in substrate and the seal substrate (for example, shown in Fig. 1 C, being formed in the groove part of substrate).
Organic electroluminescence device comprises transparent moisture absorption layer, and it can be used for positive emissive devices.Transparent moisture absorption layer comprises at least a in metal oxide and the slaine.In the particle grain size that accounts for 10% weight (D10) with account between the particle grain size (D90) of 90% weight and have about 100nm or littler difference, particularly about 50nm is to the difference of about 80nm.If the difference between D10 and the D90 is greater than 100nm, transmissivity descends so, fuzzy increasing.
Metal oxide and slaine can have about 100nm or littler, and particularly about 50nm is to the average grain diameter of about 90nm.Metal oxide and slaine can have about 30nm or bigger, and particularly about 35nm is to the minimum grain size (D of about 45nm Min), and have about 120nm or littler, the maximum particle diameter (D of particularly about 90nm to 100nm Max).If minimum grain size (D Min) less than about 30nm, may become thixotroping more and viscosity of the composition that then is used for transparent absorbed layer may increase.If maximum particle diameter (D Max) greater than about 120nm, then transmissivity reduces and fuzzy increasing.
To describe the method for compositions that is used to form transparent moisture absorption layer according to the preparation of illustrative embodiments of the invention now, wherein this layer can be used for positive surface emitting type organic electroluminescence device.
Transparent moisture absorption layer can absorb moisture and the oxygen that infiltrates through this layer, and has high-transmission rate.Thereby the metal oxide particle of nano-scale such as CaO particle should stably be dispersed in the composition that forms transparent moisture absorption layer, so that scattering does not take place the light of outgoing.Equally, because metal oxide has mixed multiple additives such as organic adhesive or inorganic bond, so particle should stably be dispersed in the composition and the solid concentration of composition should be high.
The homodisperse therein composition of the metal oxide of nano-scale or slaine prepares according to following method.
At first, metal oxide or slaine particle and solvent are to obtain dispersion.Inorganic pearl such as zirconium oxide bead also can add in the dispersion.In this case, the size of metal oxide or slaine can reduce effectively, and the risk of polluting can reduce.Pearl can have about 1mm or littler, and particularly about 0.1mm is to the particle diameter of about 0.5mm, but the particle diameter of pearl is not limited to this.Pearl is removed behind grinding step.
Dispersant can further add in the dispersion to increase the dispersion efficiency of metal oxide in the composition or slaine.
Next, dispersion is ground to form composition.Ginding process is not particularly limited, and can utilize for example coating vibrator of equipment but grind, Dyno  grinder, or Apex  grinder carries out.Grinding can about 1-60 hour, and particularly about 4-30 hour, but milling time is not limited thereto.
As mentioned above, adhesive can further add in the composition after grinding.
The average grain diameter of the metal oxide particle in the composition that obtains according to said method for about 20nm to about 300nm, and can be about 60nm about 80nm extremely.The solid concentration of composition can for about 5% weight to about 30% weight, based on the weight of composition.If the average grain diameter of metal oxide particle greater than about 300nm, is scattered in the moisture absorption layer and takes place in visible-range, cause fuzzy thus and reduce transmissivity.If the solid concentration of composition is less than about 5% weight, then the concentration of drier reduces in the final solution.If the solid concentration of composition is greater than 30% weight, then the dispersion stabilization of drier reduces in the final solution.
To describe the method according to the manufacturing organic electroluminescence device of illustrative embodiments of the invention now in detail, this device comprises the transparent moisture absorption layer that composition that utilization obtains by said method is made.
At first, comprise first electrode, the organic electroluminescent of the organic layer and second electrode partly is formed on the substrate.Then, metal oxide or slaine particle and solvent and dispersant are to obtain forming the composition of transparent moisture absorption layer.
Composition is applied on the surface, inside of seal substrate and is dry.Composition can be by dip coating, spin coated, and spraying and applying distributes or silk screen printing applies.
Dry then composition solidifies on seal substrate, to obtain transparent moisture absorption layer.Curing comprises that hot curing or UV solidify.Hot curing can be carried out in the time of about 100 ℃ to about 250 ℃.If the temperature of hot curing is greater than about 250 ℃, adhesive can decompose and getter action can take place.In addition, after hot curing, need the more time to be used for cooling.If the temperature of hot curing is less than about 100 ℃, then solvent may be retained in the moisture absorption layer and adhesive can not solidify.
Utilize transparent moisture absorption layer that said method forms can for about 0.1 μ m to about 12 μ m.Transparent moisture absorption layer has good moisture and oxygen absorption characteristic, and the organic electroluminescence device that comprises this transparent moisture absorption layer is by excellent sealing.
After preparation was formed with the seal substrate of transparent moisture absorption layer on it, sealant utilized on the outer part of the organic electroluminescent part that screen process press or distributor one of be coated in substrate and the seal substrate at least.Then, substrate combines to be formed with organic electroluminescence devices with seal substrate.
Utilize the inner space of the organic electroluminescence device of method for preparing can be placed under the vacuum or be full of inert gas.With substrate with after seal substrate combines, sealant can utilize UV light, visible light, or heat is cured.
Utilize transparent moisture absorption layer that said method forms before it absorbs moisture and keep transparent afterwards.
In organic electroluminescence device, transparent moisture absorption layer can be configured in the inner space that provides between substrate and the seal substrate.Particularly, transparent moisture absorption layer can be formed on the inner surface of the seal substrate shown in Figure 1A, be formed on the sidewall of the sealant layer shown in Figure 1B, or on the part that one of is formed in substrate and the seal substrate at least (for example, shown in Fig. 1 C, being formed in the groove part of substrate).
Figure 1A is the schematic section according to the organic electroluminescence device of illustrative embodiments of the invention.
With reference to Figure 1A, organic electroluminescence device comprises the substrate 10 that is formed by glass or transparent insulation material, organic electroluminescent part 12, and it is configured on the surface of substrate 10 and comprises first electrode, organic layer and second electrode of sequential cascade.This device comprises also and combining with substrate 10 to form the seal substrate 11 of inner space that organic electroluminescent part 12 is placed in this inner space.The inner space seals from the outside, and transparent moisture absorption layer 13 is formed on the inner surface of seal substrate 11.Transparent moisture absorption layer 13 comprises the porous oxide particle of nano-scale and has nanometer sized pores.
Substrate 10 utilizes the sealant layer 14 on the outer part that is coated in organic electroluminescent part 12 to combine with seal substrate 11.Seal substrate 11 can have for example in the shape shown in Figure 1B.
With reference to Figure 1B, the organic electroluminescence device of another exemplary comprises the substrate 20 that is formed by glass or transparent insulation material according to the present invention, organic electroluminescent part 22, and it is configured on the surface of substrate 20 and comprises first electrode of sequential cascade, the organic layer and second electrode.This device comprises also and combining with substrate 20 to form the seal substrate 21 of inner space that organic electroluminescent part 22 is placed in this inner space.The inner space seals from the outside, and transparent nano porous oxide layer 23 is configured on the sidewall of sealant layer 24.
With reference to figure 1C, the organic electroluminescence device of another exemplary comprises substrate 30 according to the present invention, has the seal substrate 31 of groove part 35 in its surface and is configured in transparent moisture absorption layer 33 in the groove part 35.The inner space that provides by substrate 30 and seal substrate 31 by sealant layer 34 from outer side seal.
With reference to figure 1D, organic electroluminescence device according to another embodiment of the invention is included as the seal substrate 41 of the glass substrate of etching and is configured in transparent moisture absorption layer 43 in the etched portions of etching glass substrate.The etching depth of etching glass substrate (h) can for about 100 μ m to about 300 μ m, but be not limited thereto.Transparent moisture absorption layer 43 can be thick to about 300 μ m for about 0.1 μ m.Organic electroluminescent part 42 is configured in the below of the transparent moisture absorption layer 43 on the substrate 40.
Transparent moisture absorption layer 13,23,33 and 43 can be thick transparent nano CaO layer.
Organic electroluminescent part 12,22,32 and 42 can form by deposition, and each comprises first electrode, the organic layer and second electrode.First electrode can be negative electrode, and second electrode can be anode.Organic layer can comprise hole injection layer, hole transmission layer, light-emitting layer, electron injecting layer, and/or electron transfer layer.
Seal substrate 11,21,31 and 41 can comprise insulating material, for example glass or transparent plastic.Protective layer can be formed on the surface, inside of seal substrate to protect this substrate not contact with moisture.Protective layer can be to warm, and chemicals and moisture have resistance. Seal substrate 11,21,31 and 41 can be used for positive emissive devices.
When being used to carry on the back emissive devices, first electrode can be transparency electrode, and second electrode can be reflecting electrode.On the other hand, when being used for positive emissive devices, first electrode can be reflecting electrode, and second electrode can be transparency electrode.First positioning of electrode is in seal substrate 11,21, and near 31 and 41, second positioning of electrode is at substrate 10,20, near 30 and 40.
Protective layer also can be formed on the upper surface of second electrode, with the complanation that allows organic electro luminescent part 12,22,32 and 42 and the resistance of chemicals and moisture is provided heat.Protective layer can comprise inorganic material for example metal oxide or metal nitride.
By seal substrate 11,21,31 and 41 and the inner spaces that limit of respective substrate 10,20,30 and 40 remain under the vacuum condition or be full of inert gas.
Transparent moisture absorption layer 13,23,33 and 43 can be thick as much as possible, as long as can obtain enough transmissivities.For example, transparent moisture absorption layer 13,23,33 and 43 can be thick to about 300 μ m for about 0.1 μ m.If thickness is less than 0.1 μ m, moisture absorption reduces.If thickness is greater than 300 μ m, then transparent moisture absorption layer 13,23,33 contacts negative electrode with 43, causes that moisture can increase in porous zone.
When seal substrate 41 was etching glass substrate shown in Fig. 1 D, transparent moisture absorption layer 43 can be thick to about 300 μ m for about 0.1 μ m.If the thickness of transparent moisture absorption layer 43 is less than 0.1 μ m, then moisture absorption reduces.If the thickness of transparent moisture absorption layer 43 is greater than 300 μ m, its etching depth (h) then, thereby transparent moisture absorption layer 43 contact negative electrodes greater than the etching glass substrate.
When seal substrate is the flat glass substrate, transparent moisture absorption layer 13,23 and 33 can for about 0.1 μ m to about 70 μ m.
As mentioned above, transparent moisture absorption layer 13,23,33 and 43 can comprise alkali metal oxide, alkaline earth oxide, metal halide, metal sulfate, metal perchlorate, and phosphorus pentoxide (P 2O 5), but be not limited thereto.The average grain diameter of particle can be about 100nm or littler, and particularly about 20 to about 100nm.
To describe the manufacture method of the organic electroluminescence device that comprises transparent moisture absorption layer of another exemplary now in detail according to the present invention.
At first, comprise first electrode of sequential cascade, the organic electroluminescent of the organic layer and second electrode partly is formed on the substrate.Then, metal oxide particle, the slaine particle, or metal oxide particle and slaine particle mix with solvent, dispersant and adhesive, to obtain forming the composition of transparent moisture absorption layer.
The composition that forms transparent moisture absorption layer can be according to following process preparation.
At first, in the metal oxide of drier or the slaine one of at least with solvent and dispersant.Then, mixture is ground to obtain comprising the dispersion of nano-scale drier.Then, dispersion is mixed the composition that forms transparent moisture absorption layer with preparation with adhesive.Each component concentrations of component and composition can be same as described above.
Form in the composition of transparent moisture absorption layer solid concentration can for about 2% weight to about 25% weight.If the solid concentration in the composition is less than about 2% weight, then the wettability power of transparent moisture absorption layer reduces.If the solid concentration in the composition is greater than 25% weight, then transmissivity reduces and fuzzy increasing.
After preparation forms the composition of transparent moisture absorption layer, composition is coated on the surface, inside of seal substrate and carries out drying.Composition can be by dip coating, spin coated, and spraying and applying distributes or silk screen printing applies, but is not limited to these methods.
When transparent moisture absorption layer utilized silk screen printing to form, adhesive in the composition and solvent played the carrier of the flowability of maintenance composition to be printed.Be used for printed compositions and can have about 500cps to about 20, the viscosity of 000cps.If the viscosity of composition is not in above-mentioned scope, then Yin Shua quality may descend.
Then, the dry compositions on seal substrate is cured to obtain transparent moisture absorption layer.Curing can comprise that for example hot curing or UV solidify.Hot curing can be carried out in the time of about 100 ℃ to about 250 ℃.If heat curing temperature is greater than about 250 ℃, then the specific area of particle reduces moisture absorption thus owing to the presintering of particle reduces, and adhesive is owing to heat is decomposed.If heat curing temperature is less than about 100 ℃, then solvent is retained in the transparent moisture absorption layer or transparent moisture absorption layer can not solidify, thereby device may suffer damage after sealing.
Transparent moisture absorption layer can be thick to about 300 μ m for about 0.1 μ m, and can absorb moisture and oxygen.
Transparent moisture absorption layer has about 95% to about 98% transmissivity and absorbs about 30% to about 50% moisture.
When transparent moisture absorption layer when to be about 100 μ m to about 300 μ m thick, it has about 95% or bigger transmissivity, generally about 96-98%, and absorb the moisture of 30-40%, and have 1.0 or littler, the generally haze value of 0.2-0.8.Utilize transparent moisture absorption layer that this method forms before it absorbs moisture and be transparent afterwards.
After preparation is formed with the seal substrate of transparent moisture absorption layer on it, sealant utilize screen process press or distributor be coated in substrate in the outer part of organic electroluminescent part and the seal substrate one of at least on.Then, substrate combines to be formed with organic electroluminescence devices with seal substrate.
In addition, utilize inner space in the organic electroluminescence device of said method manufacturing can place in a vacuum or be full of inert gas.After substrate and seal substrate combination, sealant can utilize UV light, visible light, or heat is cured.
Organic electroluminescence device can be the front emission type according to embodiments of the present invention, back of the body emission type, or two-sided emissive devices.
For the organic electroluminescence device of embodiment of the present invention, its driving method has no particular limits.Passive matrix (PM) drives and active matrix (AM) drives and can use.
Below, will the present invention be described in more detail with reference to following embodiment.Yet these embodiment just do not plan to limit the scope of the invention for explanation.
Embodiment 1
The compound siloxanes of organic/inorganic as dispersant of anhydrous calcium oxide of 100 weight portions (CaO) (average grain diameter 30 μ m) and 10 weight portions, epoxycyclohexyl trimethoxy monosilane mixes with the absolute ethyl alcohol of 400 weight portions.Then, the mixture that obtains is thus ground 24 hours to obtain the dispersion that average diameter of particles is about 70nm.This dispersion is mixed with the urethane acrylate as organic bond of 3000 weight portions, to obtain forming the composition of transparent moisture absorption layer.
Composition is printed on the etching soda-lime glass substrate, heat-treats in the time of 100 ℃ then, and UV solidifies, to form transparent moisture absorption layer.
To be formed with thereon as the epoxy coating of sealant at least a portion of soda-lime glass substrate of transparent moisture absorption layer with and on be formed with at least a portion of glass substrate of first electrode, organic layer and second electrode.Then, with two substrates in conjunction with to be formed with organic electroluminescence devices.
Fig. 2 A is scanning electron microscopy (SEM) photo that the cross section of the transparent moisture absorption layer that obtains in embodiment 1 has been described.
Fig. 2 A has confirmed that the about 106 μ m of transparent moisture absorption layer are thick, and has level in its surface, and this surface has the nano-sized metal oxide drier that is dispersed in wherein.
Fig. 3 has illustrated the transmitted spectrum of the transparent moisture absorption layer that obtains among the embodiment 1.
With reference to figure 3, almost the transmissivity with glass is consistent in whole visible-range for the transmissivity of transparent moisture absorption layer, even the thickness of transparent moisture absorption layer is greater than about 100 μ m.
Embodiment 2
Organic electroluminescence device with embodiment 1 in identical mode make, replace urethane acrylate except using tetraethoxy-silicane.
Embodiment 3
Organic electroluminescence device with embodiment 1 in identical mode make, replace urethane acrylate except using the methacrylate polysiloxanes.
Embodiment 4
Organic electroluminescence device with embodiment 1 in identical mode make, replace anhydrous calcium oxide (CaO) except using barium monoxide (BaO).
Embodiment 5
Organic electroluminescence device with embodiment 3 in identical mode make, except using phosphorus pentoxide (P 2O 5) replacement anhydrous calcium oxide (CaO).
Comparative Examples 1
Organic electroluminescence device with embodiment 3 in identical mode make, except on the top surface of soda-lime glass substrate, not forming transparent moisture absorption layer.
Comparative Examples 2
Conventional getter (Dynic HD-204) is formed on the soda-lime glass substrate.Getter also forms and is formed with first electrode thereon, at least a portion of the glass substrate of the organic layer and second electrode.Then, with two substrates in conjunction with to make organic electroluminescence device.
Comparative Examples 3
Have main particle diameter and be about 0.1 μ m or littler CaO particle (70nm) and mix, stir simultaneously to obtain solution with polyethyl methacrylate (PEMAS) as organic bond.Be printed on this solution on the etching soda-lime glass substrate and be cured to form moisture absorption layer.
To be formed with thereon as the epoxy coating of sealant at least a portion of soda-lime glass substrate of transparent moisture absorption layer with and on be formed with at least a portion of glass substrate of first electrode, organic layer and second electrode.Then, with two substrates in conjunction with to obtain organic electroluminescence device.
In the organic electroluminescence device that obtains in Comparative Examples 3, moisture absorption layer has about 85% low transmissivity and 28.7 haze value, and this represents that this layer is opaque or translucent.Although the CaO particle has the main particle diameter of 70nm, they are owing to electrostatic force becomes bulk.Thereby particle is inhomogeneous to be dispersed in the adhesive, even when particle mixes with adhesive.
Measured the transmissivity of the transparent moisture absorption layer that in embodiment 1-5, obtains.Transmissivity is 95% or bigger, and this represents that these layers are transparent and can be used for positive emissive devices.
The transparent moisture absorption layer that in embodiment 1, obtains and the moisture absorption of the getter in Comparative Examples 2 have been measured.The results are shown among Fig. 4.
The moisture that the transparent moisture absorption layer that Fig. 4 has confirmed to obtain in embodiment 1 absorbs more than and faster than the getter in the Comparative Examples 2.
The transparent moisture absorption layer that in embodiment 2,3,4 and 5, obtains have to embodiment 1 in the similar moisture-absorption characteristics of transparent moisture absorption layer that obtains; They can absorb the water greater than 30 weight portions, are 100 weight portions by original metal oxide total in the transparent moisture absorption layer.
The organic electroluminescence device that obtains in embodiment 1, Comparative Examples 1 and Comparative Examples 2 is kept under 70 ℃ and 90% the relative humidity, and along with past of time, their imagery exploitation microscope is observed.The results are shown among Fig. 5 A.
The organic electroluminescence device that obtains in embodiment 1-5 and Comparative Examples 1 and 2 is kept under 70 ℃ and 90% the relative humidity.Along with the past of time, their brightness utilizes microscope to observe.
After 500 hours under the acceleration environment of 70 ℃ and 90% relative humidity, (be equivalent to 20,000-30,000 hour real time), the brightness of the organic electroluminescence device that obtains in embodiment 1-5 keeps 90% of original intensity, and this brightness with the organic electroluminescence device (Comparative Examples 2) that uses conventional opaque drier equates or is higher.
Embodiment 6
The compound siloxanes of organic/inorganic as dispersant of anhydrous calcium oxide of 100 weight portions (CaO) (average grain diameter 30 μ m) and 10 weight portions, epoxycyclohexyl trimethoxy monosilane mixes with the absolute ethyl alcohol of 400 weight portions.Then, the mixture that obtains thus being ground 24 hours serves as that difference between about 70nm and D10 and the D90 is the dispersion of about 80nm to obtain average diameter of particles.This dispersion is mixed with the urethane acrylate as organic bond of 3000 weight portions, to obtain forming the composition of transparent moisture absorption layer.
Composition is printed on the etching soda-lime glass substrate, heat-treats in the time of 100 ℃ then, and UV solidifies, to form transparent moisture absorption layer.
To be formed with thereon as the epoxy coating of sealant at least a portion of soda-lime glass substrate of transparent moisture absorption layer with and on be formed with at least a portion of glass substrate of first electrode, organic layer and second electrode.Then, with two substrates in conjunction with to be formed with organic electroluminescence devices.
Embodiment 7
Organic electroluminescence device with embodiment 6 in identical mode make, the average grain diameter and the difference between D10 and the D90 that have about 70nm after grinding except CaO particle in the dispersion that obtains are about 60nm.
Embodiment 8
Organic electroluminescence device with embodiment 6 in identical mode make, the average grain diameter and the difference between D10 and the D90 that have about 70nm after grinding except CaO particle in the dispersion that obtains are about 70nm.
Fig. 2 B is the SEM photo in the cross section of the transparent moisture absorption layer that obtains in embodiment 6.
Fig. 2 B has confirmed that transparent moisture absorption layer is that about 100 μ m are thick, and has level in its surface, this surface have be dispersed in wherein do not have the deposition the nano-sized metal oxide drier.
Fig. 6 has illustrated the transmitted spectrum of the transparent moisture absorption layer that obtains in embodiment 6, embodiment 7, Comparative Examples 6 and the Comparative Examples 7.
With reference to figure 6, almost the transmissivity with glass is consistent in whole visible-range for the transmissivity of the transparent moisture absorption layer that obtains in embodiment 6 and embodiment 7, even the thickness of transparent moisture absorption layer is greater than about 100 μ m.
Embodiment 9
Organic electroluminescence device with embodiment 6 in identical mode make, replace anhydrous calcium oxide (CaO) except using barium monoxide (BaO).
Embodiment 10
Organic electroluminescence device with embodiment 6 in identical mode make, except using phosphorus pentoxide (P 2O 5) replacement anhydrous calcium oxide (CaO).
Comparative Examples 4
Organic electroluminescence device with embodiment 8 in identical mode make, except on the top surface of soda-lime glass substrate, not forming transparent moisture absorption layer.
Comparative Examples 5
Conventional getter (Dynic HD-204) is formed on the soda-lime glass substrate.Getter also forms and is formed with first electrode thereon, at least a portion of the glass substrate of the organic layer and second electrode.Then, with two substrates in conjunction with to be formed with organic electroluminescence devices.
Comparative Examples 6
Organic electroluminescence device with embodiment 6 in identical mode make, the average grain diameter and the difference between D10 and the D90 that have about 70nm after grinding except anhydrous calcium oxide (CaO) particle in the dispersion that obtains are about 150nm.
Comparative Examples 7
Organic electroluminescence device with embodiment 1 in identical mode make, the average grain diameter and the difference between D10 and the D90 that have about 70nm after grinding except anhydrous calcium oxide (CaO) particle in the dispersion that obtains are about 300nm.
The transmissivity and the haze value of the organic electroluminescence device that obtains in embodiment 6, embodiment 7, embodiment 8, Comparative Examples 6 and Comparative Examples 7 are listed in the table 1.
Table 1
Embodiment 6 Embodiment 7 Embodiment 8 Comparative Examples 6 Comparative Examples 7
Transmissivity (%) 95 96 95 87 78
Haze value 0.6 0.3 0.5 2.0 12.5
Reference table 1, although average grain diameter is all the same in all samples, but when the difference between D10 and the D90 be 100nm or more hour (embodiment 6, embodiment 7 and an embodiment 8) to obtain haze value be 1.0 or littler hyaline layer, and the difference between D10 and the D90 be 150nm or when bigger (Comparative Examples 6 and Comparative Examples 7) to obtain haze value be 1.0 or bigger semitransparent layer.
Be determined at the transmissivity that obtains transparent moisture absorption layer among embodiment 6, embodiment 7, embodiment 8 and the embodiment 9.Transmissivity is 95% or bigger, and this represents that these layers are transparent and can be used for positive emissive devices.
The transparent moisture absorption layer that in embodiment 8, obtains and the moisture absorption of the getter in Comparative Examples 5 have been measured.The results are shown among Fig. 4.
The moisture that the transparent moisture absorption layer that Fig. 4 has confirmed to obtain in embodiment 8 absorbs more than and faster than the getter in the Comparative Examples 5.
The transparent moisture absorption layer that in embodiment 6, embodiment 7 and embodiment 9, obtains have to embodiment 8 in the similar moisture-absorption characteristics of transparent moisture absorption layer that obtains; They can absorb the water greater than 30 weight portions, are 100 weight portions by original metal oxide total in the transparent moisture absorption layer.
The organic electroluminescence device that obtains in embodiment 8 and Comparative Examples 5 is kept under 70 ℃ and 90% the relative humidity.Along with the past of time, their imagery exploitation microscope is observed.The results are shown among Fig. 5 B.
The organic electroluminescence device that obtains in embodiment 6, embodiment 7, embodiment 8, embodiment 9, Comparative Examples 4 and Comparative Examples 5 is kept under 70 ℃ and 90% the relative humidity, along with the past of time, observes their brightness.
After 500 hours under the acceleration environment of 70 ℃ and 90% relative humidity, (be equivalent to 20,000-30,000 hour real time), the brightness of the organic electroluminescence device that obtains in embodiment 6, embodiment 7, embodiment 8 and embodiment 9 keeps 90% of original intensity, and this brightness with the organic electroluminescence device (Comparative Examples 5) that uses conventional opaque drier equates or is higher.
Embodiment 11
Mix in 57g ethanol and the 250mL gas-tight container of the anhydrous CaO powder of 3g in glove-box, form the composition of transparent moisture absorption layer with preparation.Then, zirconium oxide bead adds in the composition with being 0.3mm at 250 ℃ of down dry diameters in advance, and container is sealed to prevent to be exposed in the external environment and to be installed in the coating oscillator then.Afterwards, the material in the container was ground 18 hours.
Next, the CaO separated dispersion in pearl and the glove-box is measured the particle diameter in the dispersion.The solid concentration of the CaO dispersion that obtains thus is adjusted to about 15% weight.By dispersion is 100 weight portions, mixes with dispersion to obtain being used to form the composition of transparent moisture absorption layer as the urethane acrylate of 600 weight portions of adhesive.
The composition that obtains is printed on the etching glass substrate, heat-treats in the time of 100 ℃ then, and UV solidifies, to form transparent moisture absorption layer.
Embodiment 12
The composition that is used to form transparent moisture absorption layer prepares in the mode identical with embodiment 11, except using 51g ethanol, anhydrous CaO powder of 3g and 6g dimethyl formamide.
Embodiment 13
The composition that is used to form transparent moisture absorption layer prepares in the mode identical with embodiment 11, replaces dimethyl formamide except using methyl cellosolve.
Embodiment 14
The composition that forms transparent moisture absorption layer prepares in the mode identical with embodiment 11, replaces dimethyl formamide except using PGM.
Embodiment 15
The composition that forms transparent moisture absorption layer prepares in the mode identical with embodiment 11, replaces ethanol except using butanols.
Embodiment 16
The composition that forms transparent moisture absorption layer prepares in the mode identical with embodiment 11, replaces 57g ethanol except using 48g ethanol, and adds 9g organic/inorganic comprehensive silicon alkoxide, epoxycyclohexyl silane in addition.
Embodiment 17 and 18
The composition that forms transparent moisture absorption layer prepares in the mode identical with embodiment 16, except using organic/inorganic composite titanium alkoxide, and isopropyl titanate and organic/inorganic clad aluminum alkoxide, aluminium isopropoxide replaces organic/inorganic comprehensive silicon alkoxide polymer respectively.
Embodiment 19
Mix in the mixture of 36g ethanol and methyl cellosolve (weight ratio 1: 1) and the 250mL gas-tight container of the anhydrous CaO powder of 15g in glove-box.9g epoxycyclohexyl silane then, the compound siloxanes of organic/inorganic is added to the composition that is used to form transparent moisture absorption layer in the mixture with preparation.Then, zirconium oxide bead adds in the composition with being 0.3mm at 250 ℃ of down dry diameters in advance, and container is sealed then is exposed in the external environment preventing.Container is installed in the coating oscillator then.Secondly, the material in the container was ground 18 hours.
Next, the CaO separated dispersion in pearl and the glove-box is measured the particle diameter in the dispersion.The solid concentration of the CaO dispersion that obtains thus is adjusted to about 15% weight.
Embodiment 20
The composition that is used to form transparent moisture absorption layer prepares in the mode identical with embodiment 19, replaces organic/inorganic comprehensive silicon alkoxide polymer except using pentanedione.
Embodiment 21
The composition that is used to form transparent moisture absorption layer prepares in the mode identical with embodiment 19, except using acrylic resin (M W=8000-150000) (polyacrylate) replace organic/inorganic comprehensive silicon alkoxide polymer.
Embodiment 22
The composition that is used to form transparent moisture absorption layer prepares in the mode identical with embodiment 19, except using epoxy resin (M W=8000-150000) (polyacrylate) replace organic/inorganic comprehensive silicon alkoxide polymer.
Average grain diameter to the composition that obtains among the embodiment 11-20 is measured.The results are shown in the table 2.
Table 2
Average grain diameter (nm)
Embodiment 11 98.5
Embodiment 12 87.2
Embodiment 13 74.2
Embodiment 14 74.2
Embodiment 15 92.4
Embodiment 16 64.1
Embodiment 17 66.3
Embodiment 18 66.3
Embodiment 19 53.5
Embodiment 20 69.5
Embodiment 21 72.8
Embodiment 22 79.7
Fig. 7 and Fig. 8 are the curve chart of the particle size distribution of CaO in the composition of the transparent moisture absorption layer of formation that obtains in 14 and 20 in careful consideration.
With reference to figure 7 and Fig. 8, confirmed that particle diameter reduces when using dispersant.
Embodiment 23
The composition that obtains in embodiment 11 is printed on the soda-lime glass substrate, heat-treats to form transparent moisture absorption layer in the time of 150 ℃ then.
To be formed with thereon as the epoxy coating of sealant at least a portion of soda-lime glass substrate of transparent moisture absorption layer with and on be formed with at least a portion of glass substrate of first electrode, organic layer and second electrode.Then, with two substrates in conjunction with to be formed with organic electroluminescence devices.
Comparative Examples 8
Organic electroluminescence device is made in the mode identical with embodiment 11, except do not form transparent moisture absorption layer on the top surface of soda-lime glass substrate.
Comparative Examples 9
Conventional getter (Dynic HD-204) is formed on the top surface of soda-lime glass substrate, and epoxy resin is applied at least a portion of soda-lime glass substrate and coating is formed with first electrode thereon, at least a portion of the glass substrate of the organic layer and second electrode.Then, with two substrates in conjunction with to be formed with organic electroluminescence devices.
Be determined at the transmissivity of the transparent moisture absorption layer that obtains among the embodiment 11.Transmissivity is 95% or bigger, and this represents that this layer is transparent and can be used for positive emissive devices.
The transparent moisture absorption layer that measurement obtains in embodiment 23 and the moisture absorption of the getter in Comparative Examples 9.The moisture that the transparent moisture absorption layer that has confirmed to obtain in embodiment 23 absorbs more than and faster than the getter in the Comparative Examples 9.
The organic electroluminescence device that obtains in embodiment 23, Comparative Examples 8 and Comparative Examples 9 is kept under 70 ℃ and 90% the relative humidity, and along with past of time, their imagery exploitation microscope is observed.
Confirmed that the organic electroluminescence device that obtains had than the longer useful life of organic electroluminescence device that obtains in Comparative Examples 8 and Comparative Examples 9 in embodiment 23.
It should be apparent to those skilled in the art that various deformation and change and to obtain in the present invention, only otherwise depart from the spirit or scope of the present invention.Therefore, the present invention covers these distortion and variation, as long as they drop in the scope of claims and its equivalent.

Claims (59)

1. organic electroluminescence device comprises:
Substrate;
Seal substrate;
Place the organic electroluminescent part between substrate and the seal substrate; With
Transparent moisture absorption layer;
Wherein this transparent moisture absorption layer comprises:
At least a in about 100nm or littler metal oxide and the slaine of average grain diameter;
Adhesive; And
Dispersant.
2. according to the organic electroluminescence device of claim 1, wherein transparent moisture absorption layer forms on the sidewall that substrate is coupled to the sealant layer on the seal substrate, perhaps forms on the part one of at least in substrate and seal substrate.
3. according to the organic electroluminescence device of claim 1, wherein metal oxide and slaine are selected from alkali metal oxide, alkaline earth oxide, metal halide, metal sulfate and metal perchlorate.
4. according to the organic electroluminescence device of claim 3, wherein alkali metal oxide is lithia (Li 2O), sodium oxide molybdena (Na 2O) or potassium oxide (K 2O),
Wherein alkaline earth oxide is barium monoxide (BaO), calcium oxide (CaO) or magnesium oxide (MgO),
Wherein metal sulfate is lithium sulfate (Li 2SO 4), sodium sulphate (Na 2SO 4), calcium sulfate (CaSO 4), magnesium sulfate (MgSO 4), cobaltous sulfate (CoSO 4), gallium sulfate (Ga 2(SO 4) 3), titanium sulfate (Ti (SO 4) 2) or nickelous sulfate (NiSO 4),
Wherein metal halide is calcium chloride (CaCl 2), magnesium chloride (MgCl 2), strontium chloride (SrCl 2), yttrium chloride (YCl 2), copper chloride (CuCl 2), cesium fluoride (CsF), tantalum pentafluoride (TaF 5), fluoridize niobium (NbF 5), lithium bromide (LiBr), calcium bromide (CaBr 3), comprise cerium bromide (CeBr 4), selenium bromide (SeBr 2), bromination vanadium (VBr 2), magnesium bromide (MgBr 2), barium iodide (BaI 2) or magnesium iodide (MgI 2), and
Wherein the metal perchlorate is barium perchlorate (Ba (ClO 4) 2) or magnesium perchlorate (Mg (ClO 4) 2).
5. according to the organic electroluminescence device of claim 1, wherein metal oxide is anhydrous calcium oxide (CaO).
6. according to the organic electroluminescence device of claim 1, wherein dispersant comprises at least a following material that is selected from: low-molecular-weight organic dispersing agent, HMW organic dispersing agent, HMW organic/inorganic composite dispersing agent, low-molecular-weight organic/inorganic composite dispersing agent and organic acid.
7. according to the organic electroluminescence device of claim 1, wherein the concentration of dispersant is extremely about 100 weight portions of about 1 weight portion, is 100 weight portions by metal oxide and slaine.
8. according to the organic electroluminescence device of claim 1, wherein adhesive comprises at least a material that is selected from organic bond, inorganic bond and organic/inorganic composite adhesive.
9. according to the organic electroluminescence device of claim 1, wherein the concentration of adhesive is extremely about 5000 weight portions of about 10 weight portions, is 100 weight portions by metal oxide and slaine.
10. organic electroluminescence device according to Claim 8, wherein organic bond comprises at least a following material that is selected from: acrylic resin, methacrylic resin, polyisoprene, vinyl, epoxy resin, polyurethane resin and celluosic resin.
11. organic electroluminescence device according to Claim 8, wherein inorganic bond comprises at least a following material that is selected from: titanium dioxide, silica, zirconia, aluminium oxide and its precursor.
12. organic electroluminescence device according to Claim 8, wherein the organic/inorganic composite adhesive comprises at least a following material that is selected from: epoxy silane or derivatives thereof, vinyl silanes or derivatives thereof, amine silane or derivatives thereof, methacrylate silanes or derivatives thereof and its partly solidified product.
13. according to the organic electroluminescence device of claim 1, wherein the average grain diameter of metal oxide and slaine is about 50 to about 90nm.
14. according to the organic electroluminescence device of claim 1, wherein transparent moisture absorption layer is that about 0.1 μ m is thick to about 300 μ m.
15. according to the organic electroluminescence device of claim 1, wherein transparent moisture absorption layer has about 95% to about 98% transmissivity and about 30% to about 50% moisture absorption.
16. according to the organic electroluminescence device of claim 1, wherein when the about 100 μ m of transparent moisture absorption layer to about 300 μ m when thick, it has about 96% to about 98% transmissivity and about 30% to about 40% moisture absorption.
17. an organic electroluminescence device comprises:
Substrate;
Seal substrate;
Place the organic electroluminescent part between substrate and the seal substrate; With
Transparent moisture absorption layer,
Wherein this transparent moisture absorption layer comprises at least a in metal oxide and the slaine, and it is in the particle grain size that accounts for 10% weight (D10) and account between the particle grain size (D90) of 90% weight and have 100nm or littler difference.
18. according to the organic electroluminescence device of claim 17, wherein metal oxide and slaine have about 100nm or littler average grain diameter.
19. according to the organic electroluminescence device of claim 17, wherein metal oxide and slaine have about 30nm or bigger minimum grain size and about 120nm or littler maximum particle diameter.
20. according to the organic electroluminescence device of claim 17, wherein transparent moisture absorption layer forms on the sidewall of the sealant layer that substrate is coupled to seal substrate, perhaps forms on the part one of at least in substrate and seal substrate.
21. according to the organic electroluminescence device of claim 17, wherein metal oxide and slaine are selected from alkali metal oxide, alkaline earth oxide, metal halide, metal sulfate and metal perchlorate.
22. according to the organic electroluminescence device of claim 17, wherein alkali metal oxide is lithia (Li 2O), sodium oxide molybdena (Na 2O) or potassium oxide (K 2O),
Wherein alkaline earth oxide is barium monoxide (BaO), calcium oxide (CaO) or magnesium oxide (MgO),
Wherein metal sulfate is lithium sulfate (Li 2SO 4), sodium sulphate (Na 2SO 4), calcium sulfate (CaSO 4), magnesium sulfate (MgSO 4), cobaltous sulfate (CoSO 4), gallium sulfate (Ga 2(SO 4) 3), titanium sulfate (Ti (SO 4) 2) or nickelous sulfate (NiSO 4),
Wherein metal halide is calcium chloride (CaCl 2), magnesium chloride (MgCl 2), strontium chloride (SrCl 2), yttrium chloride (YCl 2), copper chloride (CuCl 2), cesium fluoride (CsF), tantalum pentafluoride (TaF 5), fluoridize niobium (NbF 5), lithium bromide (LiBr), calcium bromide (CaBr 3), comprise cerium bromide (CeBr 4), selenium bromide (SeBr 2), bromination vanadium (VBr 2), magnesium bromide (MgBr 2), barium iodide (BaI 2) or magnesium iodide (MgI 2), and
Wherein the metal perchlorate is barium perchlorate (Ba (ClO 4) 2) or magnesium perchlorate (Mg (ClO 4) 2).
23. according to the organic electroluminescence device of claim 17, wherein metal oxide is anhydrous calcium oxide (CaO).
24. according to the organic electroluminescence device of claim 17, wherein transparent moisture absorption layer also comprises the adhesive of about 10 weight portions to about 5000 weight portions, is 100 weight portions by metal oxide and slaine.
25. according to the organic electroluminescence device of claim 24, wherein adhesive comprises organic bond, inorganic bond, organic/inorganic composite adhesive or its mixture.
26. according to the organic electroluminescence device of claim 25, wherein organic bond comprises at least a following material that is selected from: acrylic resin, methacrylic resin, polyisoprene, vinyl, epoxy resin, polyurethane resin and celluosic resin.
27. according to the organic electroluminescence device of claim 25, wherein inorganic bond comprises at least a following material that is selected from: titanium dioxide, silica, zirconia, aluminium oxide and its precursor.
28. according to the organic electroluminescence device of claim 25, wherein the organic/inorganic composite adhesive comprises at least a following material that is selected from: epoxy silane or derivatives thereof, vinyl silanes or derivatives thereof, amine silane or derivatives thereof, methacrylate silanes or derivatives thereof and its partly solidified product.
29. according to the organic electroluminescence device of claim 17, wherein the average grain diameter of metal oxide and slaine is about 50 to about 90nm.
30. according to the organic electroluminescence device of claim 17, wherein transparent moisture absorption layer is that about 0.1 μ m is thick to about 300 μ m.
31. according to the organic electroluminescence device of claim 17, wherein transparent moisture absorption layer has about 95% to about 98% transmissivity, about 30% to about 50% wettability, and about 0.2 to about 0.8 haze value.
32. an organic electroluminescence device comprises:
Substrate;
Seal substrate;
Place the organic electroluminescent part between substrate and the seal substrate; With
Wherein transparent moisture absorption layer comprises that average grain diameter is at least a in about 100nm or littler metal oxide and the slaine, and adhesive,
Wherein the thickness of transparent moisture absorption layer is extremely about 300 μ m of about 100 μ m,
Wherein transparent moisture absorption layer has about 95% or bigger transmissivity.
33. according to the organic electroluminescence device of claim 32, wherein transparent moisture absorption layer forms on the sidewall that substrate is coupled to the sealant layer on the seal substrate, perhaps forms on the part one of at least in substrate and seal substrate.
34. according to the organic electroluminescence device of claim 32, wherein metal oxide and slaine are selected from alkali metal oxide, alkaline earth oxide, metal halide, metal sulfate and metal perchlorate.
35. according to the organic electroluminescence device of claim 34, wherein alkali metal oxide is lithia (Li 2O), sodium oxide molybdena (Na 2O) or potassium oxide (K 2O),
Wherein alkaline earth oxide is barium monoxide (BaO), calcium oxide (CaO) or magnesium oxide (MgO),
Wherein metal sulfate is lithium sulfate (Li 2SO 4), sodium sulphate (Na 2SO 4), calcium sulfate (CaSO 4), magnesium sulfate (MgSO 4), cobaltous sulfate (CoSO 4), gallium sulfate (Ga 2(SO 4) 3), titanium sulfate (Ti (SO 4) 2) or nickelous sulfate (NiSO 4),
Wherein metal halide is calcium chloride (CaCl 2), magnesium chloride (MgCl 2), strontium chloride (SrCl 2), yttrium chloride (YCl 2), copper chloride (CuCl 2), cesium fluoride (CsF), tantalum pentafluoride (TaF 5), fluoridize niobium (NbF 5), lithium bromide (LiBr), calcium bromide (CaBr 3), comprise cerium bromide (CeBr 4), selenium bromide (SeBr 2), bromination vanadium (VBr 2), magnesium bromide (MgBr 2), barium iodide (BaI 2) or magnesium iodide (MgI 2), and
Wherein the metal perchlorate is barium perchlorate (Ba (ClO 4) 2) or magnesium perchlorate (Mg (ClO 4) 2).
36. according to the organic electroluminescence device of claim 34, wherein metal oxide is anhydrous calcium oxide (CaO).
37. according to the organic electroluminescence device of claim 32, the concentration of adhesive is extremely about 5000 weight portions of about 10 weight portions in the wherein transparent moisture absorption layer, is 100 weight portions by metal oxide and slaine.
38. according to the organic electroluminescence device of claim 32, wherein adhesive comprises at least a material that is selected from organic bond, inorganic bond and organic/inorganic composite adhesive.
39. according to the organic electroluminescence device of claim 38, wherein organic bond comprises at least a following material that is selected from: acrylic resin, methacrylic resin, polyisoprene, vinyl, epoxy resin, polyurethane resin and celluosic resin.
40. according to the organic electroluminescence device of claim 38, wherein inorganic bond comprises at least a following material that is selected from: titanium dioxide, silica, zirconia, aluminium oxide and its precursor.
41. according to the organic electroluminescence device of claim 38, wherein the organic/inorganic composite adhesive comprises at least a following material that is selected from: epoxy silane or derivatives thereof, vinyl silanes or derivatives thereof, amine silane or derivatives thereof, methacrylate silanes or derivatives thereof and its partly solidified product.
42. according to the organic electroluminescence device of claim 32, wherein the average grain diameter of metal oxide and slaine is about 50 to about 90nm.
43. according to the organic electroluminescence device of claim 32, wherein transparent moisture absorption layer has about 30% to about 50% wettability, and about 0.2 to about 0.8 haze value.
44. a method for compositions for preparing the transparent moisture absorption layer that is used to form organic electroluminescence device comprises:
With at least a and solvent in metal oxide and the slaine to obtain dispersion; With this dispersion of grinding.
45. the method according to claim 44 also comprises:
Before grinding, inorganic pearl is added in the dispersion; With
After grinding, remove this inorganic pearl.
46. the method according to claim 44 also comprises:
Dispersant is added in the composition.
47. according to the method for claim 46,
Wherein this dispersant comprises:
At least aly be selected from following organic compound: acrylic resin, methacrylic resin, polyisoprene, vinylite, epoxy resin, amide resin, sulphone resin, phthalic acid ester resin, phenolate resin and celluosic resin;
At least aly be selected from following metallic alkoxide compound: silicon alkoxide, titanium alkoxide, aluminium-alcohol salt, organic/inorganic comprehensive silicon alkoxide polymer, organic/inorganic composite titanium polymer and organic/inorganic clad aluminum alkoxide polymer;
And/or pentanedione.
48. the method according to claim 44 also comprises:
After grinding, adhesive is added in the composition.
49. according to the method for claim 48,
Wherein adhesive comprises and is selected from least a of organic bond, inorganic bond and organic/inorganic composite adhesive.
50. according to the method for claim 48, wherein the concentration of adhesive is extremely about 5000 weight portions of about 10 weight portions, is 100 weight portions by metal oxide and slaine.
51. according to the method for claim 49, wherein organic bond comprises at least a following material that is selected from: acrylic resin, methacrylic resin, polyisoprene, vinyl, epoxy resin, polyurethane resin and celluosic resin.
52. according to the method for claim 49, wherein inorganic bond comprises at least a following material that is selected from: titanium dioxide, silica, zirconia, aluminium oxide and its precursor.
53. according to the method for claim 49, wherein the organic/inorganic composite adhesive comprises at least a following material that is selected from: epoxy silane or derivatives thereof, vinyl silanes or derivatives thereof, amine silane or derivatives thereof, methacrylate silanes or derivatives thereof and its partly solidified product.
54. according to the method for claim 49, wherein metal oxide and slaine comprise at least a following material that is selected from: alkali metal oxide, alkaline earth oxide, metal halide, metal sulfate, metal perchlorate and phosphorus pentoxide (P 2O 5).
55. according to the method for claim 54, wherein
Wherein alkali metal oxide is lithia (Li 2O), sodium oxide molybdena (Na 2O) or potassium oxide (K 2O),
Wherein alkaline earth oxide be barium monoxide (BaO), calcium oxide (CaO) or magnesium oxide (MgO),
Wherein metal sulfate is lithium sulfate (Li 2SO 4), sodium sulphate (Na 2SO 4), calcium sulfate (CaSO 4), magnesium sulfate (MgSO 4), cobaltous sulfate (CoSO 4), gallium sulfate (Ga 2(SO 4) 3), titanium sulfate (Ti (SO 4) 2) or nickelous sulfate (NiSO 4),
Wherein metal halide is calcium chloride (CaCl 2), magnesium chloride (MgCl 2), strontium chloride (SrCl 2), yttrium chloride (YCl 2), copper chloride (CuCl 2), cesium fluoride (CsF), tantalum pentafluoride (TaF 5), fluoridize niobium (NbF 5), lithium bromide (LiBr), calcium bromide (CaBr 3), comprise cerium bromide (CeBr 4), selenium bromide (SeBr 2), bromination vanadium (VBr 2), magnesium bromide (MgBr 2), barium iodide (BaI 2) or magnesium iodide (MgI 2), and
Wherein the metal perchlorate is barium perchlorate (Ba (ClO 4) 2) or magnesium perchlorate (Mg (ClO 4) 2).
56., wherein grind and utilize coating oscillator or grinder to carry out according to the method for claim 44.
57. according to the method for claim 44, wherein solvent comprises at least a following compound that is selected from: dimethyl formamide, ethanol, methyl alcohol, propyl alcohol, butanols, isopropyl alcohol, butanone, pure water, propylene glycol monomethyl ether (PGM), isopropyl cellulose (IPC), carrene, ethlyene dichloride, methyl cellosolve (MC) and ethyl cellosolve (EC).
58. according to the method for claim 44, wherein the solid concentration of composition is about 5% to about 30% weight, the particle in the composition has the average grain diameter of about 20nm to about 300nm.
59. an organic electroluminescence device, it utilizes the composition that is used to form transparent moisture absorption layer of the method preparation of claim 55 to make by coating and curing.
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