JP2002056971A - Sealing film for organic electroluminescent element, organic electroluminescent element using the same, and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealing film for an organic EL element restraining deterioration in the organic EL element caused by oxygen and moisture, enabled to efficiently display its luminous function, and enabling to cope with miniaturization and flattening of the organic EL element, and to provide an organic EL element using the same and manufacturing method of the same. SOLUTION: The sealing film for the organic EL element is composed of a decomposed polymer of perfluoroolefin. The organic EL element has at least a transparent electrode layer, an organic luminous material thin film layer, a metal electrode layer, and a sealing layer composed of a sealing film of the decomposed polymer of perfluoroolefin, successively laminated on a transparent substrate. The manufacturing method of the organic EL element forms the sealing film by the plasma CVD method using a gas containing perfluoroolefin as a main component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sealing film for an organic electroluminescence device (hereinafter, abbreviated as "EL"), and an organic EL device using the same.
The present invention relates to an element and a method for manufacturing the element. More specifically, the present invention provides a sealing film for an organic EL device comprising a decomposition polymer of perfluoroolefin, a sealed organic EL device having the sealing film provided on the surface, and efficiently producing the same. How to do it.

[0002]

2. Description of the Related Art An EL element utilizing electroluminescence is highly visible due to self-emission and is a completely solid state element.
Due to its characteristics such as excellent impact resistance, attention has been paid to its use as a light emitting element in various display devices. This EL element includes an inorganic EL element using an inorganic compound as a light-emitting material and an organic EL element using an organic compound. Among them, an organic EL element can significantly reduce the applied voltage. Since it is easy to reduce the size, consumes low power, can emit light in a plane, and easily emits light in three primary colors, research on its practical use as a next-generation light-emitting element has been actively made. The configuration of the light emitting portion of the organic EL element generally includes a transparent electrode layer (anode) / organic light emitting thin film layer (organic light emitting layer) / metal electrode layer (cathode) sequentially provided on a transparent substrate. Basically, this is provided with a hole injection / transport layer or an electron injection layer as appropriate, such as anode / hole injection / transport layer / organic light emitting layer / cathode, or anode / hole injection / transport layer / organic light emitting layer / electron injection. Structures such as layers / cathodes are known. The hole injection transport layer has a function of transmitting holes injected from the anode to the light emitting layer,
The electron injection layer has a function of transmitting electrons injected from the cathode to the light emitting layer. By interposing the hole injection transport layer between the light emitting layer and the anode, many holes are injected into the light emitting layer at a lower electric field, and further injected into the light emitting layer from the cathode or the electron injection layer. It is known that the collected electrons accumulate at the interface between the hole injection / transport layer and the light emitting layer because the hole injection / transport layer does not transport the electrons, thereby increasing the luminous efficiency. FIG. 1 is a principle diagram of one example of an organic EL element. As shown in FIG.
On the transparent electrode layer (anode) 2 provided thereon, an organic EL material layer 5 including a hole injection / transport layer 7, an organic light emitting layer 8, and an electron injection layer 9 is laminated, and a metal electrode layer is further formed thereon. (Cathode) 6 is laminated. Then, by passing a current between the anode and the cathode, the organic light emitting layer 8 is formed.
In this case, light emission is taken out from the transparent substrate 1 side. The organic EL element having such a configuration is a current-driven light-emitting element, and a high current must flow between the anode and the cathode in order to emit light. As a result, the element generates heat during light emission, and if there is oxygen or moisture around the element, the oxidation of the element constituent material by the oxygen or moisture is promoted, and the element is deteriorated. A typical degradation of an organic EL element due to oxidation or water is generation and growth of dark spots. A dark spot is a light emission defect point. When the oxidation of the constituent materials of the organic EL element progresses with the driving of the organic EL element, an existing dark spot grows, and eventually, an undesirable situation in which the dark spot spreads over the entire light emitting surface is caused. To cope with such a situation, various methods have been tried so far. For example, a glass, plastic or metal sealing can is bonded to a transparent substrate of an organic EL device with an adhesive, and a gas such as nitrogen gas containing barium oxide having a moisture absorbing effect is provided inside the sealing can. By filling the inert liquid with little effect on the organic EL element,
A method of forming a sealing layer and the like are used. However, in such a sealing layer, when the inside of the sealing can is filled with a gas, the volume of the gas changes depending on the environmental temperature, and as a result, a crack is formed between the sealing can and the transparent substrate. However, there is a problem that the sealing effect may not be sufficiently exhibited. In the technique of forming a sealing layer using such a sealing can, in order to hold the sealing can on a transparent substrate using an adhesive, the adhesive enters the inside of the element, Gas emission from the adhesive may damage the light emitting function of the organic EL element,
There is a problem that it is not easy to respond to recent demands for further downsizing and thinning. Therefore, instead of using the sealing can, a method of sealing the light emitting portion of the organic EL element with a heat-fusible plastic film having high moisture resistance such as a fluorine film has been attempted. However, in this method, the fluorine film is expensive and
In order to effectively exhibit moisture resistance, it is necessary to increase the film thickness, and as a result, the transparency (light transmission) of the film itself
And the light emitting ability of the light emitting body of the organic EL element is not sufficiently exhibited.

[0003]

SUMMARY OF THE INVENTION The present invention overcomes the disadvantages of the prior art relating to the sealing of an organic EL element and suppresses the deterioration of the organic EL element due to ambient oxygen and moisture. The present invention provides an organic EL device sealing film capable of effectively exhibiting the light-emitting function of the above, and also capable of responding to miniaturization and thinning of the device, an organic EL device provided with the same, and a method for efficiently manufacturing the same. It is done for the purpose of.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, using a raw material gas mainly composed of perfluoroolefin, a chemical vapor phase under discharge dissociation conditions. By performing a vapor deposition (CVD) method, it is possible to easily form a film made of the decomposition polymer of the perfluoroolefin on the light emitting portion of the organic EL device, and this film is a sealing film for the organic EL device. As a result, the present invention has been completed based on this finding. That is, the present invention provides (1) a sealing film for an organic EL element comprising a decomposition polymer of perfluoroolefin,
(2) An organic EL device in which at least a transparent electrode layer, an organic luminous body thin film layer, a metal electrode layer, and a sealing layer are sequentially laminated on a transparent substrate, wherein the sealing layer is formed by decomposition polymerization of perfluoroolefin. An organic EL element characterized in that it is a sealing film made of a material, and (3) on a laminate in which at least a transparent electrode layer, an organic luminous body thin film layer and a metal electrode layer are sequentially laminated on a transparent substrate. And forming a sealing film made of a decomposition polymer of perfluoroolefin by a chemical vapor deposition (CVD) method under a discharge dissociation condition using a source gas mainly composed of perfluoroolefin. A method for manufacturing an organic EL device.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The sealing film for an organic EL device of the present invention is made of a decomposition polymer of perfluoroolefin, and is provided on the luminous body of the organic EL device. This is for suppressing deterioration of the element due to moisture, suppressing generation and growth of dark spots, and effectively exhibiting a light emitting function. The production of this sealing film will be described in detail in a method for producing an organic EL device described later, but using a source gas mainly composed of perfluoroolefin, by a CVD method under discharge dissociation conditions,
The sealing film can be formed on the light emitting portion of the organic EL element. The thickness of the sealing film for an organic EL element of the present invention is not particularly limited, but is usually 0.01 to 10 μm, preferably 0.05 to 5 from the viewpoints of securing film strength and moisture-proof property.
μm, more preferably in the range of 0.1 to 3 μm. Next, in the organic EL device of the present invention, at least a transparent electrode layer (anode), an organic luminous body thin film layer (organic luminescent layer), a metal electrode layer (cathode), and a sealing layer were sequentially laminated on a transparent substrate. It has a structure. As the transparent substrate, 400
It is desirable that the substrate has a transmittance of 50% or more in the visible region of up to 700 nm and is smooth. Examples of such a transparent substrate include a glass plate and a polymer plate.
Preferable examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. As a polymer plate,
Examples include polycarbonate, acrylic resin, polyethylene terephthalate, polyether sulfide, and polysulfone. Of these, a glass plate is usually preferably used. The light-emitting part of the organic EL device of the present invention comprises an anode and an organic EL material layer (a hole injection transport layer, an organic light emitting layer, an electron injection layer, etc.) formed on the transparent substrate.
And a cathode, the configuration of which is:
A structure based on an anode / organic light emitting layer / cathode, which is provided with a hole injection / transport layer or an electron injection layer as appropriate, such as anode / hole injection / transport layer / organic light emitting layer / cathode or anode / hole Examples of the structure include an injection transport layer / an organic light emitting layer / an electron injection layer / a cathode. Next, the light-emitting part was composed of an organic E having a constitution of anode / hole injection / transport layer / organic light-emitting layer / electron injection layer / cathode.
The L element will be described.

The anode has a large work function (4).
eV or more) A transparent electrode using a metal, an alloy, an electrically conductive compound or a mixture thereof as an electrode material is preferably used. The sheet resistance of the anode is preferably several hundreds Ω / cm ² or less. Such materials include ITO (indium tin oxide), SnO ₂ , ZnO, and In—Zn.
Examples of the electrode material include a conductive material such as -O. In order to form this anode, a thin film may be formed from these electrode substances by a method such as a vapor deposition method or a sputtering method. The thickness of the anode is usually 10
It is selected in the range of nm to 1 μm, preferably 10 to 200 nm. The organic light emitting layer has (1) an injection function capable of injecting holes from an anode or a hole injection transport layer and applying electrons from a cathode or an electron injection layer when an electric field is applied; It has a transport function of moving electric charges (electrons and holes) by the force of an electric field, and (3) a light-emitting function of providing a field for recombination of electrons and holes inside the light-emitting layer and connecting it to light emission. . There is no particular limitation on the type of light emitting material used in the light emitting layer, and a known light emitting material in an organic EL element can be used.
Specific examples of such a luminescent material include benzothiazole-based, benzimidazole-based, benzoxazole-based fluorescent brighteners, metal chelated oxinoid compounds, styrylbenzene-based compounds, distyrylpyrazine derivatives, and aromatic dimethylidene compounds. And the like. The hole injection transport layer is a layer made of a hole transport compound,
It has the function of transmitting holes injected from the anode to the light-emitting layer.By interposing this hole injection transport layer between the anode and the light-emitting layer, many holes can be transferred to the light-emitting layer at a lower electric field. Injected. In addition, electrons injected into the light emitting layer by the cathode or the electron injection layer are accumulated near the interface in the light emitting layer due to the electron barrier existing at the interface between the light emitting layer and the hole injection transport layer, and the light emission of the EL element is reduced. Efficiency can be improved and an EL element having excellent light-emitting performance can be obtained. There is no particular limitation on the hole transporting compound used in the hole injecting / transporting layer, and any known hole transporting compound in an organic EL device can be used. Specific examples of the hole transport compound include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, and styryl Specific conductive high molecular oligomers such as anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilane compounds, aniline copolymers, and thiophene oligomers are exemplified.

The electron injection layer has a function of transmitting electrons injected by the cathode to the organic light emitting layer. There is no particular limitation on the electron transfer compound used in the electron injection layer, and a known electron transfer compound in an organic EL device can be used. Specific examples of such electron transfer compounds include nitro-substituted fluorenone derivatives, anthraquinodimethane derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimide, fluorenylidene Methane derivatives, anthrone derivatives, oxadiazole derivatives, and also metal complexes of 8-quinolinol or its derivatives, for example, tris (8-quinolinol) aluminum, bis (8-quinolinol) magnesium, bis (benzo-8-quinolinol) zinc,
Bis (2-methyl-8-quinolinol) aluminum oxide, tris (8-quinolinol) indium, tris (5-methyl-8-quinolinol) aluminum, 8
-Quinolinol lithium, tris (5-chloro-8-quinolinol) potassium, bis (5-chloro-8-quinolinol) calcium, tris (5,7-dichloro-8-)
Quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, bis (8-quinolinol) beryllium, bis (2-methyl-8-quinolinol) beryllium, bis (8-quinolinol) zinc,
Bis (2-methyl-8-quinolinol) zinc, bis (8
-Quinolinol) tin, tris (7-propyl-8-quinolinol) aluminum and the like. Note that the organic light-emitting layer, the hole injection transport layer, and the electron injection layer may be formed of one or two or more layers of each material, or two or more layers of different materials are stacked. It may be something. The above-described hole injection transport layer, organic light emitting layer, and electron injection layer are produced by forming a thin film of a material constituting them. As the method, for example, a spin coating method, a casting method,
Although there is a vapor deposition method and the like, a vacuum vapor deposition method is preferable because a uniform film is easily obtained and a pinhole is hardly generated. When this vapor deposition method is adopted for thinning the film, the vapor deposition conditions vary depending on the type of compound used, the target crystal structure of the molecular deposition film, the association structure, etc., but generally the boat heating temperature is 50 to 450 ° C. Vacuum degree 10 ^-5 -10
^-1 Pa, deposition rate 0.01-50 nm / sec, substrate temperature-
It is desirable to appropriately select a temperature within a range of 50 to 300 ° C. and a thickness of 5 nm to 1 μm. As a cathode, the work function is small (4
eV or less) A metal electrode using a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like as an electrode material is used. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium-silver alloy, Al / aluminum oxide, indium, and rare earth metals. The cathode can be manufactured by forming a thin film of these electrode substances by a method such as evaporation or sputtering. Further, the sheet resistance as an electrode is preferably several hundreds Ω / cm ² or less, and the film thickness is usually 10 nm to 1 μm, particularly 50 to 200 μm.
The range of nm is preferred.

[0008] The organic EL device of the present invention has a structure in which a perfluoroolefin is decomposed on a light-emitting portion formed of a transparent electrode (anode), an organic EL material layer, and a metal electrode (cathode) thus formed on a transparent substrate. First, an example of a method for manufacturing the above-described light-emitting portion, in which a sealing film made of a polymer is formed, will be described. After forming a transparent electrode film (anode) patterned by a method such as evaporation or sputtering on a transparent substrate such as a glass plate, the thickness is
An insulating film having a thickness of usually 0.1 to 10 μm, preferably 0.1 to 5 μm, more preferably 0.5 to 2 μm is provided by a conventionally known method. As the insulating film, a commonly used polyimide resin film may be provided, or (1) a black organic pigment and / or red, blue,
Green, purple, yellow, cyan, magenta, and at least two organic pigments selected from the group consisting of an organic pigment composed of a mixed color organic pigment that is pseudo-black, and carbon black, chromium oxide, iron oxide, titanium black, (2) a resist for forming a light-shielding film, which comprises at least one kind of light-shielding material selected from aniline black and a photosensitive resin in a solvent;
It may be provided by a photolithography method using a resist for forming a light-shielding film containing an alkali-soluble resin, a quinonediazide compound, a black pigment, and a solvent. Next, a resist pattern layer is formed by a conventionally known method via the insulating film thus provided on the transparent substrate.
The cross-sectional shape of the resist pattern layer may be any of a rectangular type and a reverse taper type. When forming a resist pattern layer having a rectangular cross-sectional shape, the photoresist used may be any of a non-chemically amplified type, a chemically amplified type, and may be any of a positive type or a negative type. . Examples of such a photoresist include (1) a non-chemically amplified positive photoresist containing an alkali-soluble novolak resin and a quinone diacid group-containing compound as essential components, and (2) a solubility in alkali due to the action of an acid. A changing resin, a chemically amplified positive photoresist containing a compound capable of generating an acid upon irradiation with radiation as an essential component, and (3) an alkali-soluble resin, an acid-crosslinkable substance, and generating an acid upon irradiation with radiation. A chemically amplified negative photoresist containing a compound as an essential component can be used. On the other hand, in the case of forming a resist pattern layer having a reverse tapered cross section, the photoresist used is, for example, Japanese Patent No. 2989
No. 064, specifically, (A) a component which crosslinks by exposure to light or by heat treatment following exposure, (B) an alkali-soluble resin, and (C) a compound which absorbs light to be exposed. Contain, and
A negative type photoresist using an alkaline aqueous solution as a developing solution can be used. There is no particular limitation on the method of providing a resist pattern layer using these photoresists, and a resist pattern layer having a rectangular or reverse tapered cross-sectional shape can be formed by a conventionally used photolithography method. . The thickness of this resist pattern layer is usually about 0.5 to several μm.

Next, after a resist pattern layer is formed on the transparent substrate having the patterned transparent electrode film via an insulating film, a hole injection / transport layer is first provided by vacuum evaporation. . In this case, the deposition conditions vary depending on the compound to be used (the material of the hole injection transport layer), the target crystal structure and the recombination structure of the hole injection transport layer, and the like. 1 × 10
^-5 to 1 × 10 ^-1 Pa, deposition rate 0.01 to 50 nm /
It is preferable that the temperature is appropriately selected within a range of seconds, a substrate temperature of −50 to 300 ° C., and a film thickness of 5 nm to 1 μm. Next, an organic light emitting layer is formed on the hole injection transport layer by a vacuum evaporation method. In this case, the deposition conditions vary depending on the compound used, but can be generally selected from the same condition ranges as in the formation of the hole injection / transport layer. Film thickness is 10-40n
The range of m is preferred. Next, an electron injection layer is provided on the organic light emitting layer by a vacuum evaporation method. In this case, the deposition conditions can be selected from the same condition ranges as those of the hole injection / transport layer and the organic light emitting layer. It is preferable that the film thickness is appropriately selected in the range of 5 nm to 1 μm. Finally, a cathode is laminated by a vacuum deposition method. The cathode is made of metal, and its thickness is preferably in the range of 50 to 200 nm. Thus, on the transparent substrate, a laminate (luminous body) composed of the transparent electrode layer (anode), the organic EL material layer (hole injection / transport layer, organic light emitting layer, electron injection layer) and the metal electrode layer (cathode) Part) is formed. FIG. 2 shows the organic E of the present invention.
It is a fragmentary sectional view showing the composition of one example of the luminous body part in L element. That is, on the transparent substrate 1 on which the patterned transparent electrode layer 2 is provided, a resist pattern layer (resin partition layer) 4 having a reverse tapered cross section is provided via an insulating film 3. An organic EL material layer having a metal electrode layer 6 on its surface (a hole injection transport layer, an organic light emitting layer, and an electron injection layer are provided in this order from the transparent electrode layer side) between the resist pattern layers. 5) is provided, and the luminous body portion is formed in a non-contact and independent state with the resist pattern layer 4. The organic EL material layer 5a having the metal electrode layer 6a on the surface is also formed on the resist pattern layer 4, although it is not necessary for the function, but for convenience in manufacturing. In the present invention, a raw material mainly composed of perfluoroolefin is formed on a laminate (light emitting portion) in which the transparent electrode layer, the organic EL material layer, and the metal electrode layer are sequentially laminated on the transparent substrate in this manner. Using a gas and a CVD method under discharge dissociation conditions (hereinafter referred to as plasma CV
According to method D), a sealing film made of a decomposition polymer of perfluoroolefin is formed, and a sealed organic EL element is manufactured. Here, the “source gas mainly composed of perfluoroolefin (hereinafter may be simply abbreviated as“ source gas ”)” means that a reactive component (a component that contributes to decomposition → polymerization) in the source gas is substantially. It means a gas consisting only of perfluoroolefin. Examples of the perfluoroolefin include a linear or branched perfluoroolefin and a perfluorocycloolefin. Further, a diluent gas can be mixed into the source gas in order to control the reactivity and enhance the handling property. The diluent gas includes a rare gas and a hydrocarbon gas. Specific examples of the rare gas include argon, helium, xenon, and the like. As the hydrocarbon gas, one having 1 to 3 carbon atoms
Are usually used, and specific examples thereof include methane,
Examples include ethylene and acetylene. Preferred diluent gases are argon, methane and ethylene. These diluent gases can be used alone or in combination of two or more. The amount of the diluent gas is usually 95% by weight or less based on the total amount with the reactive component.

The perfluoroolefin is not particularly limited, but usually has 3 to 8, preferably 4 to 6, carbon atoms.
More preferably, 5 linear or branched perfluoroolefins or perfluorocycloolefins are used.
Perfluoroolefins can be used alone or in combination of two or more, and it is particularly preferable to use one or more perfluorocycloolefins. When a perfluorocycloolefin and a linear or branched perfluoroolefin are used in combination, the amount of the linear or branched perfluoroolefin is usually 30% by weight or less, preferably 20% by weight or less of the total fluoroolefin amount. If so, a particularly high moisture-proof effect can be obtained. Examples of the linear or branched perfluoroolefin include perfluoropropene, perfluorobutene, perfluoropentene, perfluoro-2-methylbutene, and the like. Examples of the perfluorocycloolefin include perfluorocyclopropene and perfluorocycloolefin. Fluorocyclobutene, perfluorocyclopentene, perfluorocyclohexene, perfluorocycloheptene, perfluorocyclooctene, perfluoro (1-methylcyclobutene), perfluoro (3-methylcyclobutene), perfluoro (1-methylcyclopentene) ), Perfluoro (3-methylcyclopentene) and the like. Among these, perfluorocycloolefins such as perfluorocyclobutene, perfluorocyclopentene and perfluorocyclohexene are preferred, and perfluorocyclopentene is most preferred. As a method of the plasma CVD method, a conventionally known method, for example, a method described in Japanese Patent Application Laid-Open No. 9-237783 can be employed. The plasma generation conditions are usually a high frequency (RF) output of 10 W
-10 kW, temperature of workpiece 0-500 ° C, pressure 1 × 10
Perform at ^-2 to 1 × 10 ⁴ Pa. The thickness of the resulting film is generally in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm, more preferably 0.1 to 3 μm. The temperature of the object to be treated can be set arbitrarily within the above range, but by using a perfluoroolefin, the temperature of the object to be treated is 100 ° C. or less,
Preferably, the film can be formed even at 50 ° C. or lower, which is effective for improving production efficiency and suppressing damage to the substrate. As a device used for plasma CVD, a parallel plate type CVD device is generally used, but a microwave CVD device, an ECR-C
A VD device and a high-density plasma CVD device (helicon wave plasma, inductively coupled plasma, or the like) can be used. In addition, UV irradiation with a low-pressure mercury lamp or the like is performed for the purpose of promoting the dissociation of the source gas and reducing damage to the object to be treated. Ultrasonic waves can be applied to the space. In this manner, a sealing film made of a decomposition polymer of perfluoroolefin is formed on the light emitting portion of the organic EL device, and the sealed organic EL device of the present invention is obtained.

[0011]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Formation of luminous body part of organic EL element FIG. 3 is a partial cross-sectional view of a substrate for an organic EL element used in the present example.
A 3.5 μm-thick reverse tapered resin partition layer 14 is provided on a 25 × 75 × 1.1 mm-size glass plate 11 having a TO transparent electrode film 12 via a light-shielding film 13 having a thickness of 1.0 μm. It has a given structure. Using the substrate for an organic EL element, it is fixed to a substrate holder of a commercially available vapor deposition apparatus [manufactured by Nippon Vacuum Engineering Co., Ltd.], and N, N'-bis (3-methylphenyl) -N is attached to a molybdenum resistance heating boat. , N'-Diphenyl- [1,1'-biphenyl] -4,4'-diamine (hereinafter abbreviated as TPD) (200 mg) was placed in another molybdenum resistance heating boat, and 4,4'-bis (2 , 2'-
After charging 200 mg of diphenylvinyl) biphenyl (hereinafter abbreviated as DPVBi), the vacuum chamber was set to 1 × 10 ^-4 P
The pressure was reduced to a. Next, 215 boats containing TPD
Up to 220 ° C. to evaporate the TPD at a rate of 0.1 to 0.3.
The hole injection / transport layer having a thickness of 60 nm was formed by evaporation at a rate of nm / sec. The substrate temperature at this time was room temperature. The DPVBi-containing boat was heated to 240 ° C. without removing the DPVBi from the vacuum chamber, and the DPVBi was deposited at a deposition rate of 0.1 to 0.1 ° C.
Evaporation was performed on the hole injecting and transporting layer at a rate of 0.3 nm / sec to form a light emitting layer having a thickness of 40 nm. The substrate temperature at this time was also room temperature. This was taken out of the vacuum chamber, a stainless steel mask was placed on the light-emitting layer, and fixed again to the substrate holder. Then, tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was placed in a molybdenum boat. 200 mg, another 1 g of magnesium ribbon in another molybdenum boat, 500 mg of silver wire in a tungsten basket, and these boats were mounted in a vacuum tank.

Next, the pressure in the vacuum chamber is reduced to 1 × 10 ⁻⁴ Pa, and then the boat containing Alq _{3 is} heated to 230 ° C.
The Alq ₃ at a deposition rate 0.01～0.03Nm / sec deposited on the emission layer to form an electron injection layer having a thickness of 20 nm. Further, silver was vapor-deposited on the electron injection layer at a vapor deposition rate of 0.1 nm / sec. At the same time, magnesium was vapor-deposited on the electron injection layer at a vapor deposition rate of 1.4 nm / sec. By forming a cathode having a thickness of 150 nm, a light emitting portion of the organic EL device was formed. (2) Preparation of organic EL device A glass plate having a light emitting portion of the organic EL device on the surface obtained in the above (1) was used as a substrate, and was mounted on a parallel plate type plasma CVD apparatus. By performing CVD, a sealing film was formed on the luminous body. Perfluorocyclopentene (C ₅ F ₈₎ 40sccm argon 400sccm pressure 33 Pa RF power (frequency: 13.56MH _Z) by 400W substrate temperature 25 ± 3 ° C. The plasma CVD, seal consisting of decomposed polymer of perfluoro cyclopentene thickness 2μm The stop film was formed on the light emitting part with good adhesion. This film was very dense and homogeneous without generation of voids. Thus, a sealed organic EL element was produced. (3) Evaluation of organic EL device The sealed organic EL device obtained in the above (2) was
A test was conducted in which the device was left for 10,000 hours in an environment of 90 ° C. and 90% RH. When a DC voltage was applied to each of the devices before and after the leaving test by using the ITO film as an anode and the mixed metal film as a cathode, the device emitted blue light from 5 V in a light place after the leaving test, similarly to before the leaving test. Was confirmed, the visibility was extremely good, and no dark spot was observed on the light emitting surface, and the light emission was uniform. That is, it was found from the standing test that the organic EL element was hardly damaged. Example 2 Sealing was performed in the same manner as in Example 1 except that a mixture of perfluorocyclopentene and perfluoropentene in a weight ratio of 80:20 was used instead of perfluorocyclopentene in Example 1 (2). An organic EL device was prepared and evaluated. The results are the same as in Example 1,
No dark sport was observed on the light emitting surface. Comparative Example 1 In Example 1 (2), silicon nitride (SiN) was used instead of perfluorocyclopentene, and CV
The conditions were changed as follows, and a film was formed for 1 hour, and a sealed organic EL device was produced in the same manner as in Example 1.
The thickness of the sealing film was 1 μm, and the film was voided and heterogeneous. SiN 40 sccm nitrogen 250sccm pressure 33 Pa RF power (frequency: 13.56MH _Z) for 10W substrate temperature 200 ° C. The organic EL device was left standing test in the same manner as in Example 1. When a DC voltage was applied to each of the devices before and after the leaving test by using the ITO film as the anode and the mixed metal film as the cathode, the device before the leaving test was 5 in a light place.
V emitted blue light, and visibility was good. On the other hand, the device after the standing test emitted blue light from 5 V, but had low luminance and was dark enough to emit light. In addition, generation of many dark spots was observed on the light emitting surface. That is, the organic E
It was found that the L element was considerably damaged.

[0013]

The sealing film for an organic EL device of the present invention is made of a decomposition polymer of perfluoroolefin, and suppresses the deterioration of the organic EL device due to the surrounding oxygen and moisture. The light emitting function can be effectively exhibited, and the device can be made smaller and thinner.

[Brief description of the drawings]

FIG. 1 is a principle diagram of an example of an organic EL element.

FIG. 2 is a partial cross-sectional view showing a configuration of an example of a light emitting section in the organic EL device of the present invention.

FIG. 3 shows the organic E used in Example 1 and Comparative Example 1.
FIG. 3 is a partial cross-sectional view of an L element substrate.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Transparent electrode layer 3 Insulating film 4 Inverted taper type resist pattern layer 5, 5a Organic EL material layer 6, 6a Metal electrode layer 7 Hole injection transport layer 8 Organic light emitting layer 9 Electron injection layer 11 Glass plate 12 ITO Transparent electrode film 13 Light shielding film 14 Reverse tapered resin partition layer

Claims (3)

[Claims] 1. A sealing film for an organic electroluminescence element comprising a decomposition polymer of a perfluoroolefin. 2. An organic electroluminescence device comprising a transparent substrate and at least a transparent electrode layer, an organic luminous body thin film layer, a metal electrode layer and a sealing layer laminated in this order, wherein the sealing layer is a perfluoroolefin. An organic electroluminescent element, which is a sealing film made of a decomposition polymer of the above. 3. A discharge dissociation condition using a raw material gas mainly composed of perfluoroolefin, on a laminate in which at least a transparent electrode layer, an organic luminous body thin film layer and a metal electrode layer are sequentially laminated on a transparent substrate. Chemical vapor deposition (CV
A method for producing an organic electroluminescence device, wherein a sealing film made of a decomposition polymer of perfluoroolefin is formed by the method D).