JP2008016300A - Organic light emitting device, manufacturing method thereof, and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an organic lighting emitting device inexpensively and high productivity capable of suppressing or preventing time-lapse drop of the characteristics of a light emitting element, to provide an organic light emitting device manufactured by the manufacturing method, and to provide electronic equipment of high reliability that comprises the organic light emitting device. <P>SOLUTION: The organic light emitting device means comprises a substrate (one substrate) 21 on which an organic EL element 3 is formed, an upper substrate (the other substrate) 22 on which a drying agent film 4 is formed, and a sealing part 23. Its manufacturing method includes a first process in which liquid repellency is applied to a liquid repellent film formation region 221 on a closed 24 side of the upper substrate 22 where no drying agent film 4 is formed, a second process for forming the drying agent film 4 by supplying a liquid-form material containing a drying agent to a drying agent film forming region 223 of the upper substrate 22 for drying, and a third process in which the substrate 21 and the upper substrate 22 are laminated together by forming the sealing part 23. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an organic light emitting device, an organic light emitting device, and an electronic apparatus.

An electroluminescence element (organic EL element) using an organic semiconductor material is expected to be used as an organic light-emitting element provided in a solid light-emitting inexpensive large-area full-color display device, and many developments have been made (for example, , See Patent Document 1).
In general, an organic EL element has an organic semiconductor layer (organic light emitting layer) composed of an organic semiconductor material (organic light emitting material) between a cathode and an anode, and an electric field is applied between the cathode and the anode. Then, electrons are injected into the organic light emitting layer from the cathode side, and holes are injected from the anode side.

Then, the injected electrons and holes are recombined in the organic light emitting layer, and at least a part of the deactivation energy when the energy level returns from the conduction band to the valence band is released as light energy. The light emitting layer emits light.
For the purpose of improving characteristics such as light emission efficiency in such an organic EL element, active research has been conducted on the types of organic light emitting materials used, device structures, and the like.

  By the way, since the organic light emitting material is generally highly reactive with water, when it comes into contact with moisture, it will be altered and deteriorated over time. That is, the organic light emitting layer is deteriorated and deteriorated with time. For this reason, there is a problem in that the characteristics of the organic EL element, such as the light emission efficiency, are deteriorated due to the deterioration of the characteristics of the organic light emitting layer or the separation between the organic light emitting layer and the layer in contact with the organic light emitting layer. is there.

  In order to solve such problems, that is, to prevent deterioration and deterioration of the organic light emitting material, the organic EL element is sealed with a sealing material having a water vapor barrier property, and the inside of the sealing material A desiccant was placed on the organic EL element to prevent or prevent the movement (intrusion) of moisture from the outside to the inside of the organic EL element, and even if moisture entered, the moisture was absorbed by the desiccant. Device structures have been developed.

For example, Patent Document 1 proposes an organic EL element in which a concave portion is provided in the central portion, and a glass plate that can store a desiccant in the concave portion is used as a sealing material.
That is, in Patent Document 1, the organic EL element is coated with a resin material that adheres the glass substrate and the substrate on which the organic EL element is formed to the edge of the glass plate in which the desiccant is stored in the recess. The glass plate and the substrate are sealed by bonding the desiccant side and the organic EL element side facing each other and curing the resin material.

Here, as a method for forming the concave portion on the glass substrate, a blast method, a wet etching method, or the like is used.
However, it takes a long time to form the recesses using these methods, and further, for example, when a wet etching method is used, it is necessary to process the etching solution. When used as a stopper, there is a problem that the productivity of the organic EL device is lowered and the manufacturing cost is increased.
Moreover, since the desiccant stored in the recesses is localized in the central portion of the glass substrate, it is difficult to dry the entire organic EL device, and the moisture that has entered the organic EL device is sufficient. There is also a problem that it is not adsorbed by the desiccant.

JP 2000-195660 A

  An object of the present invention is to provide an organic light-emitting device capable of manufacturing an organic light-emitting device that can suppress or prevent a decrease in characteristics over time due to contact of light-emitting elements with moisture at low cost and high productivity. An object of the present invention is to provide a manufacturing method, an organic light-emitting device manufactured by the manufacturing method, and a highly reliable electronic device including the organic light-emitting device.

Such an object is achieved by the present invention described below.
The organic light emitting device manufacturing method of the present invention includes a pair of substrates facing each other, and a sealing portion that seals the pair of substrates so that a closed space is formed between the pair of substrates. A casing with;
Of the pair of substrates, an organic light emitting element including an organic light emitting layer that is provided on the closed space side of one of the substrates and is mainly composed of an organic light emitting material;
Among the pair of substrates, a manufacturing method of an organic light emitting device having a desiccant film provided on the closed space side of the other substrate and mainly composed of a desiccant,
A first step of providing liquid repellency and forming a liquid repellent film on the first region of the other substrate in the closed space where the desiccant film is not formed on the surface on the closed space side;
A liquid material containing the desiccant is supplied to a second region for forming the desiccant film on the surface of the other substrate on the closed space side, and the liquid material is supplied to the second region by the liquid repellent film. A second step of forming the desiccant film by drying in a state of being held in the region of 2,
The one substrate on which the organic light emitting element is formed and the other substrate on which the desiccant film is formed are arranged so that the organic light emitting element and the desiccant film face each other. And a third step of bonding by forming.
Thus, an organic light emitting device that can easily and reliably form a desiccant film with a predetermined pattern and thickness, and that can suppress or prevent a decrease in the characteristics of the light emitting element over time can be obtained at low cost. Thus, it can be manufactured with high productivity.

In the method for manufacturing an organic light-emitting device of the present invention, it is preferable that the first region is an outer peripheral portion of the second region.
Thereby, a desiccant film | membrane can be easily and reliably formed by predetermined thickness inside a 1st area | region.
In the method for manufacturing an organic light-emitting device of the present invention, in the first step, the liquid repellent whose main material is a compound having liquid repellency in the first region of the surface on the closed space side of the other substrate. It is preferable to impart liquid repellency by forming the film using a plasma polymerization method.
Thereby, a dense liquid repellent film can be formed in the first region on the surface of the other substrate on the closed space side, and excellent liquid repellency can be imparted.

In the manufacturing method of the organic light emitting device of the present invention, in the third step, the sealing portion is formed by solidifying a resin material supplied between the one substrate and the other substrate. It is preferable.
Thereby, a sealing part can be formed in a comparatively simple process.
In the method for manufacturing an organic light-emitting device of the present invention, prior to the third step, a compound having affinity for the resin material is used as a main material in a region where the sealing portion of the other substrate is formed. It is preferable to provide affinity for the resin material by forming a resin affinity film.
Accordingly, even when the other substrate is made of a material having low adhesion to the resin material, the other substrate and the sealing portion can be fixed with good adhesion, and the other substrate and the sealing portion can be fixed. The sealing property between the two can be improved.

In the method for manufacturing an organic light emitting device of the present invention, it is preferable that the resin material includes a gap material, and the thickness of the sealing portion is defined by the gap material.
Thereby, a closed space of a predetermined size can be provided between the one substrate and the other substrate.
In the method for manufacturing an organic light emitting device of the present invention, the gap material is preferably composed of particles.
Thereby, the separation distance between one substrate and the other substrate can be maintained at a constant size. As a result, a sealing portion having a uniform thickness can be formed, and the separation distance between the organic light emitting element and the desiccant film can be kept uniform.

In the method for manufacturing an organic light emitting device of the present invention, it is preferable that the gap material is mainly composed of a desiccant.
Thereby, since moisture can be adsorbed in the sealing portion, it is possible to more reliably prevent moisture from entering the closed space from the organic light emitting device via the sealing portion.
In the manufacturing method of the organic light-emitting device of the present invention, in the third step, the sealing portion includes a first resin material including the gap material supplied between the one substrate and the other substrate. It is preferable to form the first resin material after solidifying by supplying a second resin material not including the gap material to the opposite side of the solidified first resin material to the organic light emitting element.
Such a configuration of the sealing portion is particularly effective when applied to a case where the gap material is mainly composed of a desiccant. That is, moisture is infiltrated into the closed space from the outside of the organic light emitting device via the second sealing portion by sealing the outside of the first sealing portion with the second sealing portion. Can be suitably prevented or suppressed, and even if moisture permeates (passes through) the second sealing portion, moisture can be reliably captured by the desiccant contained in the first sealing portion. .

In the method for manufacturing an organic light emitting device according to the aspect of the invention, in the third step, the sealing portion includes the liquid repellent film formed in the first region of the surface on the closed space side of the other substrate. It is preferable that it is formed away from the desiccant film.
By adopting such a configuration, it is possible to reliably prevent alteration and deterioration of the desiccant film due to contact between the sealing portion and the desiccant film.

In the manufacturing method of the organic light-emitting device of the present invention, it is preferable that the desiccant film and the light-emitting element are brought into contact in the third step.
With this configuration, the thickness of the organic light emitting device is reduced, and when the organic light emitting element is driven, heat generated in this element is conducted through the desiccant film and the other substrate, so that the organic light emitting device There is also an advantage that heat can be efficiently radiated to the outside.

In the manufacturing method of the organic light emitting device of the present invention, the sealing portion has a water vapor permeability (specified in JIS K 7129) of 10 [g / m ² · day · 90% when the temperature of the atmosphere is 40 ° C. RH] or less.
Thereby, the function as a barrier layer which suppresses the penetration | invasion of the water | moisture content from the outer side of an organic light-emitting device to closed space can be exhibited suitably at a sealing part.

The organic light emitting device of the present invention is manufactured by the method of manufacturing an organic light emitting device of the present invention.
Thereby, a highly reliable organic light-emitting device can be obtained.
The electronic apparatus according to the present invention includes the organic light-emitting device according to the present invention.
Thereby, an electronic device with high reliability can be obtained.

Hereinafter, a method for manufacturing an organic light emitting device, an organic light emitting device, and an electronic apparatus according to the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
First, the case where the manufacturing method of the organic light-emitting device of the present invention is applied to the manufacturing method of the organic electroluminescence device will be described.
<Organic EL device>
<< First Configuration >>
First, before explaining the manufacturing method of an organic electroluminescent apparatus, the 1st structure of the organic electroluminescent apparatus obtained by applying this manufacturing method is demonstrated.

FIG. 1 is a schematic diagram (longitudinal sectional view) showing a first configuration of an organic electroluminescent device obtained by applying the method for manufacturing an organic light emitting device of the present invention. In the following description, the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.
An organic electroluminescence device (hereinafter referred to as “organic EL device”) 1 a shown in FIG. 1 includes a casing 2, an organic EL element (light emitting element) 3 provided in the casing 2, and a desiccant film 4. ing.

The casing 2 includes a substrate (one substrate) 21, an upper substrate (the other substrate) 22 disposed so as to face the substrate 21, and a closed space 24 defined between the substrates 21 and 22. As shown in the figure, the edge portion includes a sealing portion 23 that seals the substrates 21 and 22 together, and a liquid repellent film 5 that separates the sealing portion 23 and the desiccant film 4. .
The organic EL element 3 and the desiccant film 4 are provided on the upper surface of the substrate 21 and the lower surface of the upper substrate 22 in the closed space 24, respectively.

The substrate 21 serves as a support for supporting the organic EL element 3 and functions as a sealing material for hermetically sealing the organic EL element 3 and the desiccant film 4 below the organic EL element 3. To do.
In addition, since the organic EL device 1a of the present embodiment is configured to extract light from the substrate 21 (anode 31 described later) side (bottom emission type), the substrate 21 is substantially transparent (colorless transparent, colored transparent, Translucent).

For such a substrate 21, various glass material substrates and various resin substrates having translucency are preferably used.
Specifically, for example, glass materials such as quartz glass and soda glass, polyethylene terephthalate, polyethylene naphthalate, polypropylene, cycloolefin polymer, polyamide, polyethersulfone, polymethyl methacrylate, polycarbonate, polyarylate, etc. A substrate composed mainly of a resin material or the like can be used.

The upper substrate 22 serves as a support that supports the desiccant film 4 and functions as a sealing material that hermetically seals the organic EL element 3 and the desiccant film 4 on the upper side of the organic EL element 3. To do.
Since the organic EL device 1a of the present embodiment is a bottom emission type, the upper substrate 22 is not particularly required to have translucency, and a substrate composed of the above-described translucent material as a main material. In addition to a substrate that can be used, a substrate formed using a material that does not transmit light as a main material can be used.

Specifically, as a substrate composed mainly of a material that does not transmit light, a metal substrate, a resin substrate, a ceramic substrate such as alumina, and a thin film having a low water vapor transmission rate on the surface of these substrates. And a multilayer substrate coated with. Examples of the thin film having a low water vapor permeability include a SiOx film, a SiNx film, a SiON film, and a metal film.
Among these, a multilayer substrate coated with a metal substrate or a thin film having a low water vapor transmission rate is preferably used as the upper substrate 22 because it has a low water vapor transmission rate and exhibits particularly excellent water vapor barrier properties.

The sealing portion 23 defines a closed space 24 by sealing a space formed between the substrate 21 and the upper substrate 22 at these edges (sealing portion forming region 222). It functions as a sealing material that hermetically seals the organic EL element 3 and the desiccant film 4 in the space 24.
In the present embodiment, the sealing portion 23 includes a sealing material 231 and a gap material 232.

The sealing material 231 has a function of connecting the substrate 21 and the upper substrate 22.
Examples of the constituent material of the sealing material 231 include metal materials such as Al, Au, Cr, Nb, Ta, and Ti, alloys containing these metal materials, inorganic oxides such as silicon oxide, epoxy resins, acrylics, and the like. Examples thereof include resin materials such as resin, polyester resin, and polyamide resin. Among these, it is preferable to use a resin material. By using the resin material, a relatively simple process of supplying and solidifying (drying) the resin material containing the gap material 232 between the substrate 21 and the upper substrate 22 in the sealing portion forming process described later. Thus, the sealing portion 23 can be formed.

  The gap material 232 has a function of defining the thickness of the sealing portion 23, that is, the thickness of the substrate 21 and the upper substrate 22. Therefore, by supplying a resin material including the gap material 232 between the substrate 21 and the upper substrate 22 to obtain the sealing portion 23, a closed space 24 having a predetermined size is formed. It can be provided between these substrates 21 and 22.

  The shape of the gap material 232 is not particularly limited as long as it is in the form of particles. For example, the gap material 232 is preferably spherical, elliptical, or polygonal, and more preferably spherical. . By using a particulate material as the gap material 232, the separation distance between the substrate 21 and the upper substrate 22 can be maintained at a constant size in a sealing portion forming step described later. As a result, the sealing portion 23 having a uniform thickness can be formed, and the separation distance between the organic EL element 3 and the desiccant film 4 can be kept uniform.

Examples of the constituent material of the gap material 232 include metal materials such as Al, Au, Cr, Nb, Ta, and Ti, alloys containing these metal materials, inorganic oxides such as silicon oxide, and the like. One or two or more of them can be used in combination.
Further, the gap material 232 may be constituted by a desiccant in part or almost all of the gap material 232 in addition to the above-described constituent material. By configuring the gap member 232 to include a desiccant, even if moisture remains in the organic EL device 1a (closed space 24), the moisture is combined with the desiccant contained in the desiccant film 4 described later. The desiccant contained in the sealing portion 23 can be adsorbed. Furthermore, since moisture can be adsorbed (captured) in the sealing portion 23, it is possible to more reliably prevent moisture from entering the closed space 24 from the organic EL device 1a via the sealing portion 23. .

In addition, as a desiccant, the thing similar to the desiccant used with the desiccant film | membrane 4 mentioned later can be used.
The sealing part 23 having such a configuration preferably has a water vapor permeability (as defined in JIS K 7129) [g / m ² · day · 90% RH] of 10 or less when the temperature of the atmosphere is 40 ° C. 1 to 5 is more preferable. Thereby, the sealing part 23 exhibits the function as a barrier layer which suppresses the penetration | invasion of the water | moisture content from the outer side of the organic EL apparatus 1a to the closed space 24 suitably.

This moisture permeability was measured using a humidity sensor method under the conditions of the test (atmosphere) temperature (40 ± 0.5 ° C.) and the relative humidity difference (90 ± 2% RH) in accordance with JIS K 7129. Can be calculated.
In the humidity sensor method, one side of the upper substrate 22 (test piece) is saturated with water vapor, and the humidity on the opposite (low humidity) side is set to 10% RH. Next, a change in humidity due to the amount of water vapor that has passed through the test piece is detected by a humidity sensor installed on the low humidity side and converted into an electrical signal. And it is the method of calculating water vapor transmission rate from the numerical value, after measuring the water vapor transmission time of a fixed relative humidity width (90% RH) and confirming the steady state of the water vapor transmission rate.

When at least one of the substrate 21 and the upper substrate 22 is flexible, the formation of the sealing portion 23 is omitted, and after the flexible substrate is bent, the substrates are bonded to each other. By sealing at the peripheral portion to be performed, the substrate 21 and / or the upper substrate 22 can function as the sealing portion 23.
Further, when the organic EL device 1a is a flexible display having flexibility, the casing 2, that is, the substrate 21, the upper substrate 22 and the sealing portion 23 described above, are all composed of a resin material as a main material. That's fine.

  In addition, it is set as a flexible display, ie, by comprising all of the board | substrate 21, the upper board | substrate 22, and the sealing part 23 with a resin material, compared with the case where these are comprised with a glass material, for example, a casing. 2 shows a tendency for the water vapor barrier property to decrease. Therefore, it is particularly effective to apply the manufacturing method of the present invention that can form a desiccant film with a predetermined pattern and thickness, as described later, to the manufacturing method of the flexible display.

The desiccant film 4 is a desiccant film forming region (second region) 223 excluding the outer peripheral portion of the lower surface of the upper substrate 22 in the closed space 24, that is, a liquid repellent film forming region (first region) 221 described later. Is provided in a region surrounded by
The desiccant film 4 is mainly composed of a desiccant and has a function of absorbing (adsorbing) moisture remaining or entering the closed space 24. By providing such a desiccant film 4, even if moisture remains or enters the organic EL device 1 a (closed space 24), the moisture is reliably supplied to the desiccant contained in the desiccant film 4. Can be absorbed. As a result, it is possible to prevent moisture from entering into the organic EL element 3 over time, and thus it is possible to reliably prevent deterioration of the characteristics of the organic EL element 3.

Moreover, in this embodiment, as shown in FIG. 1, the desiccant film | membrane 4 is formed so that it may correspond to the shape of the organic EL element 3 mentioned later. By adopting such a configuration, the entire organic EL element 3 can be dried, and it is possible to reliably prevent moisture from locally entering a part of the organic EL element 3.
The desiccant film 4 is formed by supplying a liquid material containing a desiccant to the desiccant film forming region 223 and then drying it.

In addition, the specific example of the liquid material containing a desiccant and the formation method of the desiccant film 4 are explained in full detail in the desiccant film formation process mentioned later.
Further, the desiccant film forming region 223 is formed in the liquid repellent film forming region (first region) 221 excluding the desiccant film forming region (second region) 223 on the lower surface of the upper substrate 22 in the closed space 24. A liquid repellent film 5 is formed so as to surround it.

The liquid repellent film 5 is used when supplying a liquid material containing a desiccant and a resin material for forming the sealing portion 23 in a desiccant film forming step and a sealing portion forming step, which will be described later. The liquid material and the resin material have a function of preventing the liquid material and the resin material from protruding from the predetermined regions 223 and 222. That is, the liquid repellent film 5 has a function of holding the liquid material and the resin material in the predetermined regions 223 and 222, respectively. By adopting a configuration including such a liquid repellent film 5, it is possible to reliably obtain the desiccant film 4 and the sealing portion 23 formed with a desired pattern (shape) and thickness.
Specific examples of the material of the liquid repellent film 5 and a method for forming the material will be described in detail in the liquid repellent film forming step described later.

The organic EL element 3 is provided in a region corresponding to the closed space 24 on the substrate 21.
As shown in FIG. 1, the organic EL element (light emitting element) 3 includes an anode 31, a cathode 33, and an organic semiconductor layer 32 provided between the anode 31 and the cathode 33.
The organic semiconductor layer 32 is I: a laminate in which a hole transport layer, an organic light emitting layer, and an electron transport layer are laminated in this order from the anode 31 side, and a hole transport layer or an electron transport layer from a configuration of II: I. Any structure may be used as long as it includes an organic light emitting layer such as a laminate in which any of the above is omitted, and a single layer body in which the hole transport layer and the electron transport layer are omitted from the configuration of III: I, The case of I will be described as a representative.

The anode 31 is an electrode that injects holes into the organic semiconductor layer 32 (in this embodiment, a hole transport layer).
As a constituent material (anode material) of the anode 31, a conductive material having translucency is selected because the organic EL device 1a has a bottom emission structure in which light is extracted from the anode 31 side. Those having high conductivity are preferably used.

Examples of the constituent material of the anode 31 include indium tin oxide (ITO), fluorine-containing indium tin oxide (FITO), antimony tin oxide (ATO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), and tin oxide. Examples include transparent conductive materials such as (SnO ₂ ), zinc oxide (ZnO), fluorine-containing tin oxide (FTO), fluorine-containing indium oxide (FIO), and indium oxide (IO), and at least one of these materials Can be used.
Such an anode 31 has a light transmittance (visible light region) of preferably 60% or more, more preferably 80% or more. Thereby, light can be efficiently extracted from the anode 31 side.

On the other hand, the cathode 33 is an electrode that injects electrons into the organic semiconductor layer 32 (in this embodiment, an electron transport layer).
As a constituent material (anode material) of the cathode 33, a material having a small work function is particularly preferable among those exhibiting excellent conductivity for the purpose of improving the efficiency of injecting electrons into the electron transport layer. Used.

Examples of the constituent material of the cathode 33 include alkali metals made of Li, Na, K, Rb, Cs and Fr, and alkaline earth metals made of Be, Mg, Ca, Sr, Ba and Ra. 1 type or 2 types or more of them can be used in combination.
Further, when an alloy containing a metal as described above is used as a constituent material of the cathode 33, an alloy containing a stable metal such as Ag, Al, or Cu, specifically, an alloy such as MgAg, AlLi, or CuLi. May be used. By using such an alloy as the constituent material of the cathode 33, it is possible to improve the injection efficiency of electrons into the electron transport layer and the stability of the cathode 33.

As described above, the organic semiconductor layer 32 in which the hole transport layer, the organic light emitting layer, and the electron transport layer are stacked in this order from the anode 31 side is provided between the anode 31 and the cathode 33.
The hole transport layer has a function of transporting holes injected from the anode 31 to the organic light emitting layer.
As a constituent material (hole transport material) of this hole transport layer, for example, polyethylene dioxythiophene: polystyrene sulfonate, polyaniline: polystyrene sulfonate, polyarylamine, fluorene-arylamine copolymer, fluorene-bithiophene copolymer , Poly (N-vinylcarbazole), polyvinylpyrene, polyvinylanthracene, polythiophene, polyalkylthiophene, polyhexylthiophene, poly (p-phenylenevinylene), polytinylenevinylene, pyreneformaldehyde resin, ethylcarbazole formaldehyde resin or derivatives thereof, etc. These can be used, and one or more of these can be used in combination.

In addition, you may make it provide the hole injection layer which improves the hole injection efficiency from the anode 31, for example between the anode 31 and a hole transport layer.
As a constituent material (hole injection material) of this hole injection layer, for example, copper phthalocyanine, 4,4 ′, 4 ″ -tris (N, N-phenyl-3-methylphenylamino) triphenylamine ( m-MTDATA) and the like.

The electron transport layer has a function of transporting electrons injected from the cathode 33 to the organic light emitting layer.
As a constituent material (electron transport material) of the electron transport layer, for example, benzene such as 1,3,5-tris [(3-phenyl-6-tri-fluoromethyl) quinoxalin-2-yl] benzene (TPQ1) Compounds, naphthalene compounds, phenanthrene compounds, chrysene compounds, perylene compounds, anthracene compounds, pyrene compounds, acridine compounds, stilbene compounds, thiophene compounds such as BBOT, butadiene compounds, coumarin compounds , Quinoline compounds, bistyryl compounds, pyrazine compounds such as distyrylpyrazine, quinoxaline compounds, benzoquinone compounds such as 2,5-diphenyl-para-benzoquinone, naphthoquinone compounds, anthraquinone compounds, 2- ( 4-biphenylyl) -5- Oxadiazole compounds such as 4-t-butylphenyl) -1,3,4-oxadiazole (PBD), triazole compounds such as 3,4,5-triphenyl-1,2,4-triazole Compounds, oxazole compounds, anthrone compounds, fluorenone compounds such as 1,3,8-trinitro-fluorenone (TNF), diphenoquinone compounds such as MBDQ, stilbenequinone compounds such as MBSQ, anthraquinodimethane Compounds, thiopyrandioxide compounds, fluorenylidenemethane compounds, diphenyldicyanoethylene compounds, fluorene compounds, pyrrole compounds, phosphine oxide compounds, 8-hydroxyquinoline aluminum (Alq ₃ ), benzoxazole, Benzothiazole Include various metal complexes, such as complexes with ligands it is, can be used singly or in combination of two or more of them.

For example, an electron injection layer that improves the efficiency of electron injection from the cathode 33 to the electron transport layer may be provided between the cathode 33 and the electron transport layer.
Examples of the constituent material (electron injection material) of the electron injection layer include 8-hydroxyquinoline, oxadiazole, or derivatives thereof (for example, metal chelate oxinoid compounds containing 8-hydroxyquinoline). These can be used alone or in combination of two or more.

  Here, when an electric current is applied between the anode 31 and the cathode 33 (voltage is applied), holes that have moved in the hole transport layer are injected into the organic light emitting layer, and electrons that have moved in the electron transport layer are organic. It is injected into the light emitting layer, and holes and electrons are recombined in this organic light emitting layer. Then, excitons (excitons) are generated in the organic light emitting layer, and energy (fluorescence or phosphorescence) is emitted (emitted) when the excitons return to the ground state.

As a constituent material (organic light emitting material) of the organic light emitting layer, for example, 1,3,5-tris [(3-phenyl-6-tri-fluoromethyl) quinoxalin-2-yl] benzene (TPQ1), 1,3 , 5-tris [{3- (4-t-butylphenyl) -6-trisfluoromethyl} quinoxalin-2-yl] benzene (TPQ2), phthalocyanine, copper phthalocyanine (CuPc), iron phthalocyanine Low molecular weight compounds such as metal or metal-free phthalocyanine compounds such as tris (8-hydroxyquinolinolate) aluminum (Alq ₃ ), factory (2-phenylpyridine) iridium (Ir (ppy) ₃ ) Oxadiazole polymers, triazole polymers, carbazole polymers, fluorene polymers Examples thereof include macromolecules such as molecules, and these can be used alone or in combination. Various polymer materials and various low molecular materials can be used alone or in combination.

In the organic EL device 1 a as described above, the desiccant film 4 is formed on the lower surface of the upper substrate 22. Therefore, even if moisture remains or enters the organic EL device 1a (closed space 24), it is possible to prevent the moisture from adsorbing to the desiccant and entering the organic EL element 3 over time. The deterioration of the characteristics of the organic EL element 3 can be suitably suppressed or prevented.
Further, by forming the liquid repellent film 5 in the liquid repellent film forming region 221 on the lower surface of the upper substrate 22, the desiccant is applied by the liquid repellent film 5 in the desiccant film forming process and the sealing part forming process described later. When the liquid material to be contained and the resin material for forming the sealing portion 23 are supplied, these can be reliably prevented from protruding from a predetermined region. As a result, the desiccant film 4 and the sealing portion 23 are formed with a predetermined pattern and thickness. Therefore, the desiccant film 4 can reliably function as a desiccant, and the sealing portion 23 reliably prevents moisture from entering the organic EL device 1a (closed space 24). Can do.

  Further, by forming the liquid repellent film 5 in the liquid repellent film forming region 221 on the lower surface of the upper substrate 22, the desiccant film 4 can be formed without providing a recess in the upper substrate 22. As a result, it is possible to reduce the thickness of the upper substrate 22 and to set the thickness of the organic EL element 3 as a whole. Further, compared to the case where the concave portion is provided on the upper substrate 22, the region for forming the desiccant film 4 can be set larger, that is, the desiccant film 4 can be formed in a region including the organic EL element 3. The entire closed space 24 can be reliably dried.

  FIG. 1 shows the case where one organic EL element 3 is provided on the substrate 21, but this is schematically shown, and the present invention is not limited to such a case. The EL element 3 may be provided on a substrate, and a plurality of pixels may be formed by these elements. Further, in this case, the desiccant film 4 may be individually provided on the lower surface of the upper substrate 22 so as to correspond to each organic EL element 3, and includes each organic EL element 3. It may be provided integrally.

The organic EL device 1a described above can be used for, for example, a display, but can also be used as a light source or the like, and can be used for various optical applications.
When the organic EL device 1a is applied to a display, the driving method is not particularly limited, and any of an active matrix method and a passive matrix method may be used.

Next, the manufacturing method of the organic light emitting device of the present invention will be described by taking as an example the case where the first configuration of the organic EL device, that is, the organic EL device 1a shown in FIG. 1 is manufactured.
FIG. 2 is a view (perspective view and longitudinal sectional view) for explaining a method of manufacturing the organic EL device shown in FIG. 1, and FIG. 3 is a schematic view showing a plasma polymerization apparatus for forming a liquid repellent film. FIG. 4 is a perspective view showing a mask used for plasma polymerization. In the following description, the upper side in FIGS. 2 to 4 is referred to as “upper” and the lower side is referred to as “lower”.
The manufacturing method of the first configuration of the organic EL device includes: [1A] organic EL element forming step, [2A] liquid repellent film forming step, [3A] desiccant film forming step, and [4A] sealing portion formation. Process. Hereinafter, each of these steps will be described sequentially.

[1A] Organic EL Element Formation Step The organic EL element 3 is formed on the substrate 21.
(1A-1) First, the substrate 21 is prepared, and the anode 31 is formed on the substrate 21.
The anode 31 is, for example, a chemical vapor deposition method (CVD) such as plasma CVD, thermal CVD, or laser CVD, a dry plating method such as vacuum deposition, sputtering, or ion plating, or a wet method such as electrolytic plating, immersion plating, or electroless plating. It can be formed by using a plating method, a thermal spraying method, a sol-gel method, a MOD method, a metal foil bonding, or the like.

(1A-2) Next, a hole transport layer is formed on the anode 31.
For example, the hole transport layer may be dried (desolvent or dedispersed) after supplying the hole transport layer forming material obtained by dissolving the above-described hole transport material in a solvent or dispersing in a dispersion medium onto the anode 31. Medium).
Examples of the method for supplying the hole transport layer forming material include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, and spray coating. Various coating methods such as a printing method, a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method can be used. By using such a coating method, the hole transport layer can be formed relatively easily.

Examples of the solvent or dispersion medium used for preparing the hole transport layer forming material include inorganic solvents such as ammonia, hydrogen peroxide, and water, ketone solvents such as methyl ethyl ketone (MEK) and acetone, methanol, ethanol, and isopropanol. Alcohol solvents such as diethyl ether and diisopropyl ether, cellosolve solvents such as methyl cellosolve and ethyl cellosolve, aliphatic hydrocarbon solvents such as hexane and pentane, and aromatic carbonization such as toluene, xylene and benzene Examples thereof include various organic solvents such as hydrogen solvents, aromatic heterocyclic compound solvents such as pyridine and pyrazine, and mixed solvents containing these.
The drying can be performed, for example, by standing in an atmospheric pressure or a reduced pressure atmosphere, heat treatment, or blowing an inert gas.

(1A-3) Next, an organic light emitting layer is formed on the hole transport layer (on the side opposite to the anode 31).
For example, the organic light-emitting layer is dried (desolvent or dedispersion medium) after supplying the organic light-emitting layer forming material obtained by dissolving the above-described organic light-emitting material in a solvent or dispersing in a dispersion medium onto the hole transport layer. ).
The method for supplying the organic light emitting layer forming material and the method for drying are the same as described in the formation of the hole transport layer.

  In the case of using the organic light emitting material as described above, a nonpolar solvent is suitable as the solvent or dispersion medium used for preparing the organic light emitting layer forming material, for example, xylene, toluene, cyclohexylbenzene, dihydrobenzofuran. , Aromatic hydrocarbon solvents such as trimethylbenzene and tetramethylbenzene, aromatic heterocyclic solvents such as pyridine, pyrazine, furan, pyrrole, thiophene and methylpyrrolidone, aliphatic carbonization such as hexane, pentane, heptane and cyclohexane Examples thereof include hydrogen solvents, and these can be used alone or as a mixed solvent containing them.

(1A-4) Next, an electron transport layer is formed on the organic light emitting layer (on the side opposite to the hole transport layer).
The electron transport layer is dried (desolvent or dedispersion medium) after supplying the electron transport layer forming material obtained by, for example, dissolving the above electron transport material in a solvent or dispersing in a dispersion medium onto the organic light emitting layer. Can be formed.
The solvent or dispersion medium used for the preparation of the electron transport layer forming material, the method for supplying the electron transport layer forming material, and the drying method are the same as described in the formation of the hole transport layer.
(1A-5) Next, the cathode 33 is formed on the electron transport layer (on the side opposite to the organic light emitting layer).
The cathode 33 can be formed by using, for example, a vacuum deposition method, a sputtering method, bonding of metal foil, application and firing of metal fine particle ink, or the like.
The organic EL element 3 is formed on the substrate 21 through the above steps.

[2A] Liquid repellent film forming step (first step)
Next, an upper substrate 22 is prepared, and as shown in FIG. 2A, a liquid repellent film is formed excluding the sealing portion forming region 222 and the desiccant film forming region (second region) 223 on the upper substrate 22. The liquid repellent film 5 is formed in the region 221, that is, the liquid repellent film forming region (first region) 221 in which the desiccant film 4 is not formed on the upper substrate 22 in the closed space 24.

In other words, in this embodiment, the outer peripheral portion of the desiccant film formation region (second region) 223 forms a liquid repellent film formation region (first region) 221, and this region on the upper substrate 22 is repelled. A liquid film 5 is formed.
Here, in the liquid repellent film forming region 221 of the upper substrate 22, the wettability with respect to the liquid material containing the dry material is lowered by forming the liquid repellent film 5. Further, since the resin material is generally a highly lyophilic material, by forming the liquid repellent film 5 in the liquid repellent film forming region 221 of the upper substrate 22, the liquid repellent film forming region 221 of the upper substrate 22 is The wettability with respect to the resin material is lower than in other regions, and the resin material does not substantially adhere.

Therefore, by forming the liquid repellent film 5 in the liquid repellent film forming region 221 on the upper substrate 22, in the desiccant film forming process [3A] and the sealing part forming process [4A] described later, respectively. The liquid material and resin material to be used can be suitably prevented or suppressed from adhering to this region 221.
A method for forming (depositing) the liquid repellent film 5 in the liquid repellent film forming region 221 is not particularly limited. For example, I: a liquid repellent film formed by depositing a compound having liquid repellency by plasma polymerization. And II: a method of obtaining the liquid repellent film 5 by chemically bonding a liquid repellent coupling agent onto the substrate. According to the method I, the dense liquid repellent film 5 can be formed on the substrate, and even when the thickness is set relatively thin, the liquid repellent film 5 is provided with excellent liquid repellency. Can do. Further, according to the method II, the liquid repellent film 5 can be obtained by a relatively simple process of supplying a liquid repellent coupling agent and drying the substrate without using a large-scale apparatus such as a vacuum chamber. Can be formed.

Hereinafter, the case where the liquid repellent film 5 is formed using the methods I and II will be described.
I: Method for Obtaining Liquid Repellent Film 5 by Forming Liquid Repellent Compound by Plasma Polymerization FIG. 3 shows an example of a plasma polymerization apparatus for forming the liquid repellent film 5.
A plasma polymerization apparatus 100 shown in FIG. 3 includes a vacuum chamber 103 to which a vacuum pump 101 and a gas supply pipe 102 are connected, and an electrode 104 that also serves as a sample stage and a gas supply pipe 102 are supplied into the vacuum chamber 103. And a head 105 for injecting gas.

The electrode 104 is provided below the vacuum chamber 103 and is connected to a high frequency power source 106 disposed outside the vacuum chamber 103. In the plasma polymerization apparatus 100, the upper wall 107 of the vacuum chamber 103 is grounded, and functions as a counter electrode with respect to the electrode 104.
When the liquid repellent film 5 is formed by plasma polymerization, a voltage is applied between the electrode 104 and the upper wall 107 by operating the high frequency power source 106. At this time, when an electric field is generated in the vacuum chamber 103 and a source gas is supplied together with a carrier gas from a gas supply pipe 102 described later, a discharge occurs and plasma of the source gas is generated.

The head 105 is provided above the vacuum chamber 103 and connected to the gas supply pipe 102.
A gas cylinder (not shown) that is filled and supplied with a carrier gas is connected to the gas supply pipe 102 via a flow control valve, and a raw material container (not shown) that stores the raw material of the plasma polymerization film is connected via the flow control valve. ing.

The vaporized source gas and carrier gas are sucked by the negative pressure in the vacuum chamber 103, supplied to the head 105 through the gas supply pipe 102, and discharged from the head 105 into the vacuum chamber 103 in the form of a mist.
Note that the flow rates of the source gas and the carrier gas supplied to the vacuum chamber 103 are controlled by opening and closing operations of the flow rate control valve.
The liquid repellent film 5 as described above is formed by the plasma polymerization apparatus 100 as follows.

(2AI-1) First, the upper substrate 22 is disposed on the electrode 104 in the vacuum chamber 100, and the mask 108 is placed on the upper substrate 22.
As the mask 108, for example, as shown in FIG. 4, the first portion 109 that contacts the desiccant film forming region 223, the second portion 110 that contacts the sealing portion forming region 222, and these first portions What has the some beam part 111 constructed so that it may not contact the upper board | substrate 22 between the part 109 and the 2nd part 110 is used.

When such a mask 108 is used, the liquid-repellent film 5 having a desired shape can be formed without forming a resist mask in a complicated process such as photolithography, so that the process can be simplified. it can.
Further, the beam portion 111 is laid so as not to contact the upper substrate 22, that is, the beam portion 111 is laid on the side opposite to the upper substrate 22 in the thickness direction of the mask 108, so Can be made to reach the upper substrate 22. As a result, the liquid repellent film 5 corresponding to the shape of the sealing portion forming region 222 can be formed without cutting the liquid repellent film 5 at the position where the beam portion 111 is provided.
Further, since the mask 108 can be used repeatedly, the cost for the mask can be reduced.

(2AI-2) Next, a compound having liquid repellency as a raw material of the liquid repellent film 5 is stored in a raw material container.
As the raw material, a compound having liquid repellency and capable of being formed by plasma polymerization is used. For example, in addition to fluorinated hydrocarbons such as trifluoromethane and octafluorocyclobutane, sulfur hexafluoride is used.

(2AI-3) Next, by operating the vacuum pump 101 to reduce the pressure in the vacuum chamber 103, the carrier gas and the source gas are supplied into the vacuum chamber 104 through the supply pipe 102 and the head 105. A voltage is applied between the electrode 104 and the upper wall 107 by operating the high frequency power source 106.
As a result, discharge occurs in the vacuum chamber 107, and as a result, the source gas is turned into plasma. Then, the molecules of the plasma source gas collide with each other to cause a polymerization reaction between them, and the liquid-repellent film forming region 221 on the upper substrate 22 is composed of a product generated by the polymerization reaction. A liquid repellent film 5 is formed.
The liquid repellent film 5 formed by such plasma polymerization, for example, when trifluoromethane is used as a raw material, has a general formula — (CF ₂ ) _n — [ _{where n} represents an integer of 1 or more. In particular, it has a high density and exhibits excellent liquid repellency.

In this plasma polymerization, the output of the high-frequency power source is preferably about 100 to 600 W, and more preferably about 200 to 400 W.
The flow rates of the carrier gas and the source gas are preferably about 10 to 80 sccm, and more preferably about 30 to 50 sccm.
The pressure in the vacuum chamber is preferably about 1 to 70 Pa, and more preferably about 20 to 50 Pa.
The film formation time is preferably about 10 to 120 seconds, and more preferably about 30 to 60 seconds.
By performing film formation under such conditions, the liquid repellent film 5 having excellent liquid repellency can be formed.

II: Method for obtaining the liquid repellent film 5 by chemically bonding a liquid repellent coupling agent on the substrate In this method, the liquid repellent coupling agent may be a functional group having liquid repellent properties. And a reactive group that binds to the upper substrate 22 are preferably used. By using such a coupling agent, the bonding force between the upper substrate 22 and the coupling agent becomes strong, and the liquid repellent film 5 can be formed on the upper substrate 22 with good adhesion.

Here, the liquid repellent coupling agent is referred to as “first coupling agent”, the liquid repellent functional group of this compound and the reactive group that binds to the upper substrate 22 are respectively referred to as “first coupling agent”. 1 functional group "and" first reactive group ".
At least one first reactive group may be contained in the first coupling agent, but a plurality of first reactive groups are preferably contained. Thereby, the 1st coupling agent and upper substrate 22 can be combined with a plurality of 1st reactive groups, and the adhesiveness to the upper substrate 22 of the 1st coupling agent can be improved.

  The first reactive group is not particularly limited as long as it can be bonded to the upper substrate 22. For example, when the hydroxyl group is exposed on the surface of the upper substrate 22, for example, an alkoxy group or a halogen atom is used. Examples thereof include hydrolyzable groups such as groups, amino groups and the like. Among these, when a plurality of first reactive groups are provided, it is preferable to include a hydrolyzable group. Thereby, in addition to the upper substrate 22, the first reactive groups can be bonded to each other, so that a network (network structure) by the first coupling agent can be formed on the upper substrate 22. Thus, the formed liquid repellent film 5 becomes dense. As a result, particularly high liquid repellency can be obtained and adhesion to the upper substrate 22 of the liquid repellent film 5 can be improved.

As a 1st functional group, what contains a fluoroalkyl group, an alkyl group, a vinyl group etc. is mentioned, for example, Especially, the thing containing a fluoroalkyl group is preferable. The functional group containing a fluoroalkyl group has particularly excellent liquid repellency.
Further, the weight average molecular weight of the functional group having liquid repellency is preferably about 200 to 4000, and more preferably about 1000 to 2000.

  In consideration of the above, as the first sex compound, when the hydroxyl group is exposed on the surface of the upper substrate 22, for example, the first sex compound includes a functional group including a fluoroalkyl group, and includes Si, Ti, Al, A coupling agent having Zr or the like can be preferably used, and among them, a silane coupling agent having a functional group containing a fluoroalkyl group is particularly preferable. Such a silane coupling agent is inexpensive and easily available.

Here, the silane coupling agent having a functional group containing a fluoroalkyl group is represented by the general formula R _n SiX _(4-n) (where X is a hydrolyzable group that generates a silanol group by hydrolysis, and R is fluoro. A functional group including an alkyl group, and n is an integer of 1 to 3, and preferably an integer of 1 or 2.
In this general formula, examples of X include a methoxy group, an ethoxy group, and a halogen group.

A plurality of Rs or Xs may be the same as or different from each other.
Specific examples of such a silane coupling agent having a functional group containing a fluoroalkyl group include tridecafluoro-1,1,2,2 tetrahydrooctyltriethoxysilane, tridecafluoro-1,1,2, 2 tetrahydrooctyltrimethoxysilane, tridecafluoro-1,1,2,2 tetrahydrooctyltrichlorosilane, trifluoropropyltrimethoxysilane and the like.

  Further, the supply of the first coupling agent to the liquid repellent film forming region 221 on the surface of the upper substrate 22 can be performed by various processes such as a liquid phase process and a gas phase process. It is preferable to carry out. According to the liquid phase process, the first coupling agent is prepared by a relatively simple process of preparing a liquid material containing the first coupling agent and supplying the liquid material to the liquid repellent film forming region 221. The liquid repellent film forming region 221 on the upper substrate 22 can be reliably supplied.

Examples of the liquid phase process include various coating methods such as a droplet discharge method such as an ink jet method, a spin coating method, a casting method, and a micro gravure coating method, and one or more of these are combined. Can be used. Among these, it is preferable to use a droplet discharge method. According to this method, the liquid material can be selectively supplied to the liquid repellent film forming region 221 relatively easily and with excellent accuracy.
Hereinafter, a liquid material containing a silane coupling agent having a functional group containing a fluoroalkyl group (hereinafter simply referred to as “silane coupling agent”) is supplied to the liquid repellent film forming region 221 by an inkjet method. The case where the liquid repellent film 5 is formed will be described as an example.

(2AII-1) First, a liquid material containing a silane coupling agent is prepared.
Various solvents are used as the solvent for dissolving the silane coupling agent. For example, aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene, tetramethylbenzene, and cyclohexylbenzene can be used.
(2AII-2) Next, a liquid material is supplied to the liquid repellent film forming region 221 on the surface of the upper substrate 22 by an inkjet method.

(2AII-3) Next, the upper substrate 22 is heated, for example, to hydrolyze the hydrolyzable group of the silane coupling agent, and the generated silanol group and the hydroxyl group exposed on the surface of the upper substrate 22 To form a siloxane bond. Thereby, as shown in FIG. 2A, the liquid repellent film 5 corresponding to the shape of the liquid repellent film forming region 221 is formed on the surface of the upper substrate 22.
Then, the first functional group having liquid repellency is exposed on the surface of the liquid repellent film 5, thereby exhibiting liquid repellency.

At this time, a siloxane bond is also formed between silanol groups of adjacent silane coupling agents. Thereby, the adhesiveness of the liquid repellent film 5 is improved.
The heating temperature at the time of heating is preferably about 50 to 200 ° C, and more preferably about 80 to 150 ° C.
The heating time is preferably about 1 to 50 minutes, and more preferably about 5 to 20 minutes.

[3A] Desiccant film forming step (second step)
Next, as shown in FIG. 2B, the desiccant film 4 is formed in the desiccant film formation region 223 on the upper substrate 22.
In the method for manufacturing an organic light emitting device according to the present invention, the desiccant film 4 supplies a liquid material containing a desiccant to the desiccant film forming region 223 surrounded by the liquid repellent film forming region 221 on the upper substrate 22. The liquid material is formed by drying (desolvent or dedispersion medium).

Here, when the desiccant is mainly composed of a sticky or adhesive compound, a liquid material containing such a desiccant is supplied to the desiccant film forming region 223 and dried to dry the region 223. The desiccant film 4 is formed by adhering the agent.
Further, when the desiccant is mainly composed of a compound having no tackiness and adhesiveness, the liquid material containing the desiccant and the resin material is supplied to the desiccant film forming region 223 and dried. The desiccant film 4 in which the desiccant is supported by the resin material in the region 223 is formed. In addition, as a resin material contained in a liquid material, the thing similar to the resin material demonstrated by the following process [4A] can be used.

  Therefore, even if the desiccant is mainly composed of a compound having tackiness or adhesiveness, or the desiccant is composed of a compound having no tackiness and adhesiveness, the drying on the upper substrate 22 is performed. Although the desiccant film 4 can be formed in the agent film forming region 223, it is preferable that the desiccant film is mainly composed of the former. Thereby, since it is not necessary to contain materials other than the desiccant in the desiccant film 4, it is possible to impart excellent hygroscopicity to the desiccant film 4, and the desiccant itself has adhesiveness or adhesiveness. Therefore, the desiccant film 4 can be formed without the desiccant peeling off from the upper substrate 22.

The desiccant used for the desiccant film 4 is not particularly limited. For example, a desiccant that chemically adsorbs (chemically adsorbs) water contained in the closed space 24 (in the atmosphere) And desiccants that adsorb (physically adsorb). Among these, a desiccant that chemisorbs is preferable. By using such a desiccant, even if conditions such as the temperature in the closed space 24 change, the water adsorbed on the desiccant can be reliably supported without being desorbed.
In consideration of the above, as the desiccant, a compound having tackiness or adhesiveness and chemically adsorbing water is preferably used. Specifically, the desiccant is represented by the general formula of the following chemical formula 1. And the like are preferably used.

［式中、Ｒは、炭素数１以上のアルキル基、アルケニル基、アリール基、複素環基、アシル基を表し、Ｍは、３価の金属元素を表し、ｎは、１以上の整数を表す。］

[Wherein R represents an alkyl group having 1 or more carbon atoms, an alkenyl group, an aryl group, a heterocyclic group, or an acyl group, M represents a trivalent metal element, and n represents an integer of 1 or more. . ]

When this compound reacts with water molecules, the MO bond in the compound is cleaved (hydrolyzed), and two hydroxyl groups, that is, —OH bonds, are generated to chemically adsorb water.
Here, in the compound represented by the general formula of Chemical Formula 1, as described above, R represents an alkyl group, alkenyl group, aryl group, heterocyclic group, or acyl group having 1 or more carbon atoms.

The alkyl group may be linear or cyclic. Specifically, examples of the linear alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the alkyl group include a cyclopentyl group, a cyclohexyl group, a norbonane group, an adamantane group, and the like.
As an alkenyl group, a vinyl group, an allyl group, a butenyl group, etc. are mentioned, for example.

Examples of the aryl group include a phenyl group, a tolyl group, a biphenyl group, and a naphthyl group.
Examples of the heterocyclic group include a pyrrole group, a pyrroline group, a pyrazole group, and a pyrazoline group.
Examples of the acyl group include a formyl group, an acetyl group, a propionyl group, and a butyryl group.

Further, the substituent R as described above may be one in which at least a part of the hydrogen atoms contained in the substituent is substituted with another element.
M represents a trivalent metal element, and specific examples thereof include Al, La, Y, and Ga.
Therefore, specific examples include, for example, compounds represented by the following chemical formulas 2 and 3 as the compounds represented by the general formula of the chemical formula 1 above.

［式中、ｎは、１以上の整数を表す。］

[Wherein n represents an integer of 1 or more. ]

Examples of the desiccant that does not have tackiness or adhesiveness and physically adsorb water include silica gel A type, silica gel B type, natural zeolite, synthetic zeolite, allophane, and sepionite.
Moreover, as a desiccant which does not have adhesiveness or adhesiveness and chemically adsorbs water, for example, metal oxides such as sodium oxide (Na ₂ O), potassium oxide (KO ₂ ), and calcium oxide (CaO) , Lithium sulfate (Li ₂ SO ₄ ), sodium sulfate (Na ₂ SO ₄ ), sulfates such as calcium sulfate (CaSO ₄ ), calcium chloride (CaCl ₂ ), magnesium chloride (MgCl ₂ ), strontium chloride (SrCl ₂₎ ), Metal halides such as barium perchlorate (Ba (ClO ₄ ) ₂ ), and perchlorates such as magnesium perchlorate (Mg (ClO ₄ ) ₂ ).
The above desiccant may be used individually by 1 type, and may be used in combination of 2 or more types. Moreover, you may use together what has adhesiveness or adhesiveness, and what does not have.

  The content of the desiccant in the liquid material is preferably about 100 to 10000 mg / L, and more preferably about 300 to 5000 mg / L. When the content of the desiccant is less than the above range, it becomes difficult to form the desiccant film 4 with a sufficient thickness, and the resulting desiccant film 4 may have insufficient effects as a desiccant. . Moreover, when there is more content of a desiccant than the said range, there exists a possibility that the applicability | paintability of a liquid material may become poor and it may become difficult to form a desiccant film with uniform thickness.

Examples of the solvent or dispersion medium for preparing the liquid material containing the desiccant include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, pentane, heptane, and cyclohexane. Is mentioned.
The method for supplying the liquid material to the desiccant film formation region 223 on the upper substrate 22 and the method for drying are the same as described in the hole transport layer forming step in the step [1A].

The coating amount of the liquid material is preferably in the range of about 1.0~10.0μL / cm ^2, more preferably about 2.0~4.0μL / cm ^2. Thereby, the desiccant film 4 excellent in the drying effect can be formed on the upper substrate 22.
The drying temperature is preferably about 100 to 250 ° C, and more preferably about 150 to 200 ° C.

The drying time is preferably about 5 to 120 minutes, and more preferably about 10 to 40 minutes.
In the present embodiment, as shown in FIG. 1, the desiccant film 4 is such that the lower surface of the desiccant film 4 is not in contact with the upper surface of the organic EL element 3 (surface opposite to the organic semiconductor layer side of the cathode). Although the case where the thickness is set has been described, the thickness may be set so as to be in contact with the upper surface of the organic EL element 3. With this configuration, the thickness of the organic EL device 1a is reduced, and at the time of driving the organic EL element 3, the heat generated by this element is conducted through the desiccant film 4 and the upper substrate 22 to form the organic EL element 1a. There is also an advantage that heat can be efficiently radiated to the outside of the EL device 1a.

When the lower surface of the desiccant film 4 is in contact with the upper surface of the organic EL element 3, the liquid repellent film 5 is set thinner than the thickness of the desiccant film 4. Thereby, the lower surface of the desiccant film 4 can be reliably brought into contact with the upper surface of the organic EL element 3.
Specifically, the thickness of the desiccant film 4 is preferably about 1.0 to 6.0 μm, and more preferably about 2.0 to 4.0 μm.

By forming the desiccant film 4 in the formation process as described above, the upper substrate 22 is subjected to a special process such as a counterbore process, and the desiccant film 4 is formed on the surface of the upper substrate 22 without forming a recess. Can be formed. Therefore, as shown in the liquid repellent film forming step [2A], the step applied to the surface of the upper substrate 22 can be simplified, and the manufacturing cost can be reduced.
In addition, according to the method for manufacturing an organic light emitting device of the present invention, the liquid repellent film 5 is formed in the liquid repellent film forming region 221, so that the liquid repellent film 5 allows the liquid material containing the desiccant to be the desiccant film. Since it can be prevented from protruding from the formation region 223, the desiccant film 4 can be reliably formed at a predetermined thickness inside the liquid repellent film formation region 221. Therefore, it is possible to form the desiccant film 4 that can efficiently remove the water remaining or entering the organic EL device 1a (closed space 24). Furthermore, even if the sealing part 23 is made of a material that is easily altered or deteriorated by the desiccant film 4, the desiccant film 4 and the sealing part 23 can be formed without contacting each other. The deterioration / deterioration of the desiccant film 4 due to the contact between them can be reliably prevented.

[4A] Sealing part forming step (third step)
Next, as shown in FIG. 2 (d), the substrate 21 and the upper substrate 22 are bonded together by forming a sealing portion 23 that seals the substrate 21 and the upper substrate 22 at their edges.
In the present embodiment, the sealing portion 23 is configured by the sealing material 231 and the gap material 232 as described above, but in the following, a case where the sealing material 231 is configured by a resin material is taken as an example. A process for forming the portion 23 will be described.

(4A-1) First, as shown in FIG. 2C, a resin material (sealing material 231) containing the gap material 232 is supplied to the sealing portion forming region 222 of the upper substrate 22.
In this manufacturing method, the liquid repellent film 5 is formed in the liquid repellent film forming region 221 in the step [2A]. Therefore, the liquid repellent film 5 can suitably prevent the resin material supplied to the sealing portion forming region 222 from protruding from the region 222. Therefore, in the next step (4A-2), sealing is performed. The portion 23 can be reliably formed with a predetermined pattern and thickness.

(4A-2) Next, as shown in FIG.2 (d), the board | substrate 21 and the upper board | substrate 22 respectively oppose the side in which the desiccant film | membrane 4 was formed, and the side in which the organic EL element 3 was formed. Then, bonding is performed with the resin material (sealing material 231) interposed, and the resin material is solidified (dried) to be bonded. Here, the resin material includes a gap material 232. Therefore, since the gap material 232 can define the separation distance between the substrate 21 and the upper substrate 22, the sealing portion 23 having a desired thickness can be formed by setting the size of the gap material 232. it can.
In addition, it is preferable to perform this sealing part formation process [4A] in the dry atmosphere by inert gas (for example, dry nitrogen) or dry air from which moisture was removed as much as possible. Thereby, the penetration | invasion of the water | moisture content to the organic EL apparatus 1a (closed space 24) can be reliably prevented in this sealing process.

Through the steps as described above, the organic EL device 1a is formed.
In such a manufacturing method, the desiccant film 4 is formed on the surface (flat surface) of the upper substrate 22 without performing a special process such as a counterbore process that forms a concave (counterbore) portion on the upper substrate 22. That is, since the desiccant can be carried, the processing applied to the upper substrate 22 is simplified. Therefore, the productivity of the organic EL device can be improved and the manufacturing cost can be reduced.

  In the present embodiment, the case where the desiccant film 4 is formed so as to correspond to the shape of the organic EL element 3 has been described. However, the present invention is not limited to such a case, and the desiccant film 4 described in the present embodiment. May be divided. The desiccant film having such a form is formed by providing liquid repellency on the upper substrate 22 so as to surround the outside of the region where the divided desiccant film is formed.

<< Second Configuration >>
Next, a second configuration of the organic EL device will be described.
Hereinafter, the second configuration of the organic EL device will be described with a focus on differences from the first configuration, and description of similar matters will be omitted.
FIG. 5 is a schematic diagram (longitudinal sectional view) showing a second configuration of the organic EL device obtained by applying the method for manufacturing the organic light emitting device of the present invention. In the following description, the upper side in FIG. 5 is referred to as “upper” and the lower side is referred to as “lower”.

The organic EL device 1b shown in FIG. 5 is the same as the organic EL device 1a of the first embodiment except that the configuration of the sealing portion 23 is different.
That is, the first sealing portion 23a configured by the sealing material 231 and the gap material 232, and the organic EL element 3 of the first sealing portion 23a configured by the sealing material 231 without including the gap material 232 The organic EL device 1a is the same as that of the first embodiment except that the second sealing portion 23b provided in contact with the opposite side is provided.

Here, the first sealing portion 23 a has the same configuration as the sealing portion 23 described in the first configuration, and the second sealing portion 23 b extends from the sealing portion 23 to the gap material 232. Is omitted. In other words, the outer peripheral portion of the sealing portion 23 described in the first configuration is surrounded by the sealing material 231.
In this organic EL device 1b, the same operation and effect as described in the organic EL device 1a of the first embodiment can be obtained.

  In addition, it is especially effective to apply the sealing portion 23 to such a configuration when the gap material 232 is mainly composed of a desiccant. That is, the outside of the first sealing portion 23a is sealed with the second sealing portion 23b, so that the inside of the closed space 24 is formed from the outside of the organic EL device 1b via the second sealing portion 23b. It is possible to suitably prevent or suppress the ingress of moisture into the water, and even if moisture permeates (passes through) the second sealing portion 23b, the desiccant (gap) contained in the first sealing portion 23 Moisture can be reliably captured (adsorbed) by the material 232).

Next, a manufacturing method of the second configuration of the organic EL device shown in FIG. 5, that is, a manufacturing method of the organic light emitting device of the present invention will be described.
Hereinafter, the manufacturing method of the second configuration will be described with a focus on differences from the manufacturing method of the first configuration, and description of the same matters will be omitted.
FIG. 6 is a view (perspective view) for explaining a method of manufacturing the second configuration of the organic EL device shown in FIG. In the following description, the upper side in FIG. 6 is referred to as “upper” and the lower side is referred to as “lower”.

  The manufacturing method of the second configuration of the organic EL device is similar to the manufacturing method of the first configuration, [1B] organic EL element forming step, [2B] liquid repellent film forming step, and [3B] desiccant. A film forming step and a [4B] sealing portion forming step. In the sealing portion forming step [4B], the first sealing portion 23a is formed between the substrate 21 and the upper substrate 22. Thereafter, the second sealing portion 23b is formed on the opposite side of the first sealing portion 23b from the organic EL element 3, and is the same as described in the manufacturing method of the first configuration.

Hereinafter, this sealing part formation process [4B] is demonstrated.
[4B] Sealing Part Formation Step (4B-1) First, as shown in FIG. 6A, the surface of the upper substrate 22 is exposed at the edge of the sealing part forming region 222 of the upper substrate 22. A resin material (sealing material 231) containing the gap material 232 is supplied.

(4B-2) Next, as shown in FIG.6 (b), the board | substrate 21 and the upper board | substrate 22 are made to respectively oppose the side in which the desiccant film | membrane 4 was formed, and the side in which the organic EL element 3 was formed. After bonding together with the resin material interposed, the resin material is solidified (dried) and bonded by forming the first sealing portion 23a.
(4B-3) Next, as shown in FIG. 6C, the side opposite to the organic EL element 3 of the first sealing portion 23a formed at the edge portion of the substrate 21 and the upper substrate 22, that is, After the resin material not containing the gap material 232 (sealing material 231) is supplied so as to surround the first sealing portion 23a, the resin material is solidified (dried), and the second sealing is performed. A portion 23b is formed.

By passing through the above processes, the sealing part 23 comprised by the 1st sealing part 23a and the 2nd sealing part 23b is formed.
By adopting such a configuration for the sealing portion 23, it is possible to suitably prevent or suppress moisture from entering the closed space 24 from the outside of the organic EL device 1b by the second sealing portion 23b. Furthermore, even if moisture passes (permeates) through the second sealing portion 23b, the moisture can be reliably adsorbed (captured) by the desiccant contained in the first sealing portion 23.

<< Third Configuration >>
Next, a third configuration of the organic EL device will be described.
Hereinafter, the third configuration of the organic EL device will be described with a focus on differences from the first configuration, and description of similar matters will be omitted.
FIG. 7 is a schematic view (longitudinal sectional view) showing a third configuration of the organic EL device obtained by applying the method for manufacturing the organic light emitting device of the present invention. In the following description, the upper side in FIG. 7 is referred to as “upper” and the lower side is referred to as “lower”.

In the organic EL device 1c shown in FIG. 7, the sealing material 231 is made of a resin material, and the resin affinity having an affinity for the resin material (sealing material 231) is formed in the sealing portion forming region 222 of the upper substrate 22. The organic EL device 1a is the same as that of the first embodiment except that the film 6 is formed.
In this organic EL device 1c, the same operation and effect as the organic EL device of the first embodiment can be obtained.

  Moreover, in this organic EL device 1c, since the resin affinity film 6 is formed in the sealing portion forming region 222 on the upper substrate 22, the adhesion between the upper substrate 22 and the sealing portion 23 (resin material). Will be improved. Therefore, even if the upper substrate 22 is made of a material having low adhesion to the sealing material 231 (for example, a metal material), the sealing portion 23 is attached to the upper substrate 22 via the resin affinity film 6. It can be fixed (fixed) with good adhesion. Thereby, the airtightness in the interface of the upper board | substrate 22 and the sealing part 23 improves, and the penetration | invasion of the water | moisture content in the organic EL apparatus 1c (closed space 24) can be prevented or suppressed more suitably.

Next, a manufacturing method of the third configuration of the organic EL device shown in FIG. 7, that is, a manufacturing method of the organic light emitting device of the present invention will be described.
Hereinafter, the manufacturing method of the third configuration will be described with a focus on differences from the manufacturing method of the first configuration, and description of similar matters will be omitted.
The method of manufacturing the third configuration of the organic EL device includes the [1C] organic EL element forming step, the [2C] liquid repellent film forming step, the [3C] resin affinity film forming step, and the [4C] desiccant film. And a [5C] sealing portion forming step. In the resin affinity film forming step [3C], the resin affinity film 6 is formed in the sealing portion forming region 222 on the upper substrate 22. The method is the same as that described in the manufacturing method of the first configuration, except that the resin material is given affinity. That is, it is the same as that described in the manufacturing method of the first configuration, except that the resin affinity film forming step [3C] is provided prior to the sealing portion forming step [5C] (third step).

Hereinafter, the resin affinity film forming step [3C] will be described.
[3C] Resin affinity film forming step The resin affinity film 6 is formed in the sealing member forming region 222 of the upper substrate 22 to impart affinity to the resin material.
In the present specification, “having affinity with a resin material” means that the reactivity or interaction with the resin material is high.

The sealing portion forming region 222 is given affinity for the resin material by forming the resin affinity film 6 having affinity for the resin material in the sealing portion forming region 222 on the upper substrate 22. be able to.
Such a resin affinity film 6 can be formed by, for example, chemically coupling a coupling agent having affinity for the resin material to the sealing portion forming region 222 on the upper substrate 22.

Hereinafter, a method for forming the resin affinity film 6 using a coupling agent having a lyophilic property to the resin material will be described.
In this method, instead of the coupling agent having liquid repellency, a coupling agent having affinity for the resin material is used, and the coupling agent having this affinity is supplied to the sealing portion forming region 222. The method II is the same as that described in the step [2A] except that the resin affinity film 6 is formed in this region 222 on the upper substrate 22.

In such a method, as the coupling agent having affinity for the resin material, one having a functional group having affinity for the resin material and a reactive group that binds to the upper substrate 22 is preferably used. .
When such a compound is supplied to the sealing portion forming region 222 on the surface of the upper substrate 22, the reactive group of the compound is bonded to the upper substrate 22. Thereby, the resin affinity film 6 can be formed in the sealing portion forming region 222 with good adhesion.

Here, the coupling agent having an affinity for the resin material is referred to as “second coupling agent”, the functional group having an affinity for the resin material of this compound, and the reactivity to bind to the upper substrate. The groups may be referred to as “second functional group” and “second reactive group”, respectively.
The second reactive group may be the same as the first reactive group described above, and it is preferable that a plurality of the second reactive groups are included in the second coupling agent. Is a structure in which a hydroxyl group is exposed on the surface thereof, it preferably contains a hydrolyzable group.

  The second functional group is not particularly limited. For example, when the resin material (sealing material 231) is mainly composed of an epoxy resin, for example, an azole group such as an imidazole group or a triazole group, an amino group, Examples include those containing an epoxy group and a vinyl group. Among these, those containing an amino group or an azole group are particularly preferable. Since the functional group containing these groups has particularly excellent affinity (reactivity, interaction) for the epoxy resin, the second coupling agent is used for the sealing portion 23. It exhibits excellent adhesion.

Further, when the resin material (sealing material 231) is mainly composed of an acrylic resin, it is particularly preferable to select a material containing a phosphate group as the second functional group. Since the functional group containing this group has particularly excellent affinity for the acrylic resin, the second coupling agent has excellent adhesion to the sealing portion 23. Become.
Moreover, it is preferable that the weight average molecular weight of a 2nd functional group is about 200-4000, and it is more preferable that it is about 1000-2000.

Considering the above, when the sealing material 231 is made of an epoxy resin, a silane coupling agent having a functional group containing an amino group or an azole group is used as the second coupling agent. Is preferred.
Specific examples of such a silane coupling agent having a functional group containing an amino group or an azole group include N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N- 2 (aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, etc. are mentioned, and those containing an azole group include, for example, PA-2 (manufactured by Nikko Materials), IS-1000 (Nikko Materials). And those included in IM-1000 (manufactured by Nikko Materials Co., Ltd.).

When the resin material (sealing material 231) is mainly composed of an acrylic resin, it is preferable to use a silane coupling agent having a functional group containing a phosphate group as the second coupling agent.
Specific examples of such a silane coupling agent having a functional group containing a phosphate group include those contained in F-100 (manufactured by Denki Kagaku Kogyo Co., Ltd.).

Further, as a method of supplying the second coupling agent to the sealing portion forming region 222, the same method as described in the method of supplying the first coupling agent to the liquid repellent film forming region 221 is used. Can do.
As described above, the liquid repellent film forming region 221 and the sealing portion forming region 222 which are two regions on the surface of the upper substrate 22 are provided without providing a bank such as a resist layer on the upper substrate (base material) 22. In addition, the liquid repellent film 5 and the resin affinity film 6 can be formed, respectively, and the time required for film formation and the manufacturing cost can be reduced.

The order of the liquid repellent film forming step [2C] and the lyophilic film forming step [3C] is not limited to the above-described case, and the steps [2C] and [3C] are almost the same. The step [3C] may be performed prior to the step [2C].
With this configuration, the resin affinity film 6 is formed in the sealing portion forming region 222 of the upper substrate 22 in the sealing portion forming step [5C], which is a subsequent step. Can be formed with good adhesion.

In the manufacturing method of the third configuration, the same operation and effect as the manufacturing method of the first configuration can be obtained.
In the manufacturing method of the third configuration, since the resin affinity film 6 is formed in the sealing portion forming region 222 on the upper substrate 22, the upper substrate 22 is in close contact with the sealing material 231. Even if it is a case where it consists of material (for example, metal material) with low property, the sealing part 23 can be fixed to the upper board | substrate 22 with sufficient adhesiveness. As a result, the hermeticity of the interface between the upper substrate 22 and the sealing portion 23 is improved, and an organic EL device in which moisture permeation into the organic EL device 1c (closed space 24) is suitably prevented or suppressed is obtained. Can do.

<Electronic equipment>
Such organic EL devices (organic light-emitting devices of the present invention) 1a and 1b can be incorporated into various electronic devices.
FIG. 8 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied.

In this figure, a personal computer 1100 includes a main body 1104 provided with a keyboard 1102 and a display unit 1106 provided with a display. The display unit 1106 is rotatable with respect to the main body 1104 via a hinge structure. It is supported by.
In the personal computer 1100, the display unit 1106 includes the organic EL devices 1a to 1e described above.

FIG. 9 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the present invention is applied.
In this figure, a cellular phone 1200 includes a plurality of operation buttons 1202, an earpiece 1204 and a mouthpiece 1206, and a display unit.
In the mobile phone 1200, the display unit includes the organic EL devices 1a to 1e described above.

FIG. 10 is a perspective view showing the configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.
Here, an ordinary camera sensitizes a silver halide photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an imaging device such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.

A display unit is provided on the back of a case (body) 1302 in the digital still camera 1300, and is configured to display based on an imaging signal from the CCD, and functions as a finder that displays an object as an electronic image.
In the digital still camera 1300, the display unit includes the organic EL devices 1a to 1e described above.

A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.
A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).
When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.

  In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the data communication input / output terminal 1314 as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

  In addition to the personal computer (mobile personal computer) in FIG. 10, the mobile phone in FIG. 9, and the digital still camera in FIG. 8, the electronic apparatus of the present invention includes, for example, a television, a video camera, a viewfinder type, Monitor direct-view video tape recorder, laptop personal computer, car navigation system, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, video phone, security TV Monitors, electronic binoculars, POS terminals, devices equipped with touch panels (for example, cash dispensers and automatic ticket vending machines for financial institutions), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographs, ultrasound diagnostic devices, internal Endoscopic display device), fish finder, various measuring instruments Instruments (e.g., gages for vehicles, aircraft, and ships), a flight simulator, various monitors, and a projection display such as a projector. The electronic device of the present invention may have only a light emitting function that does not have a display function.

As mentioned above, although the manufacturing method of the organic light-emitting device, organic light-emitting device, and electronic device of this invention were demonstrated based on embodiment of illustration, this invention is not limited to these.
For example, in the method for manufacturing an organic light-emitting device of the present invention, one or more optional steps may be added as necessary.
Moreover, the organic light-emitting device of the present invention may be a combination of any two or more configurations (features) of the above-described embodiments.

Further, the organic light emitting device of the present invention may be configured to extract light from the upper substrate side (top emission type). In this case, a material having translucency is used as the material of the upper substrate.
Furthermore, the structure of each part of the organic light-emitting device of the present invention can be replaced with an arbitrary one that can exhibit the same function, or an arbitrary structure can be added.

It is the schematic diagram which showed the 1st structure of the organic electroluminescent apparatus obtained by applying the manufacturing method of the organic light-emitting device of this invention. It is a figure for demonstrating the method to manufacture the 1st structure of an organic electroluminescent apparatus with the manufacturing method of the organic light-emitting device of this invention. It is a schematic diagram which shows the plasma polymerization apparatus used with the manufacturing method of the organic light-emitting device of this invention. It is a perspective view which shows the mask used when forming a liquid repellent film | membrane by plasma polymerization. It is the schematic diagram which showed the 2nd structure of the organic electroluminescent apparatus obtained by applying the manufacturing method of the organic light-emitting device of this invention. It is a figure for demonstrating the method to manufacture the 2nd structure of an organic electroluminescent apparatus with the manufacturing method of the organic light-emitting device of this invention. It is the schematic diagram which showed the 3rd structure of the organic electroluminescent apparatus obtained by applying the manufacturing method of the organic light-emitting device of this invention. 1 is a perspective view showing a configuration of a mobile (or notebook) personal computer to which an electronic apparatus of the present invention is applied. It is a perspective view which shows the structure of the mobile telephone (PHS is also included) to which the electronic device of this invention is applied. It is a perspective view which shows the structure of the digital still camera to which the electronic device of this invention is applied.

Explanation of symbols

  1a, 1b, 1c ... Organic EL device 2 ... Casing 21 ... Substrate 22 ... Upper substrate 221 ... Liquid repellent film forming region 222 ... Sealing portion forming region 223 ... Desiccant film forming region 23 ... Sealing portion 23a …… First sealing portion 23b …… Second sealing portion 231 …… Sealing material 232 …… Gap material 24 …… Closed space 3 …… Organic EL element 31 …… Anode 32 …… Organic semiconductor layer 33 ... Cathode 4 ... Desiccant film 5 ... Liquid repellent film 6 ... Resin affinity film 100 ... Plasma polymerization apparatus 101 ... Vacuum pump 102 ... Gas supply pipe 103 ... Vacuum chamber 104 ... Electrode 105... Head 106... High-frequency power source 107... Upper wall 108... Mask 109... First part 110 ... Second part 111. …… Keyboard 1104 …… Main body 1106 …… Display unit 1200 …… Mobile phone 1202 …… Operation buttons 1204 …… Earpiece 1206 …… Speaker 1300 …… Digital still camera 1302 …… Case (body) 1304 …… Light receiving unit 1306 …… Shutter button 1308 …… Circuit board 1312 …… Video signal output terminal 1314 …… Input / output terminal for data communication 1430 …… TV monitor 1440 …… Personal computer

Claims (14)

A casing provided with a pair of substrates facing each other and a sealing portion for sealing the pair of substrates so that a closed space is formed between the pair of substrates;
Of the pair of substrates, an organic light emitting element including an organic light emitting layer that is provided on the closed space side of one of the substrates and is mainly composed of an organic light emitting material;
Among the pair of substrates, a manufacturing method of an organic light emitting device having a desiccant film provided on the closed space side of the other substrate and mainly composed of a desiccant,
A first step of providing liquid repellency and forming a liquid repellent film on the first region of the other substrate in the closed space where the desiccant film is not formed on the surface on the closed space side;
A liquid material containing the desiccant is supplied to a second region for forming the desiccant film on the surface of the other substrate on the closed space side, and the liquid material is supplied to the second region by the liquid repellent film. A second step of forming the desiccant film by drying in a state of being held in the region of 2,
The one substrate on which the organic light emitting element is formed and the other substrate on which the desiccant film is formed are arranged so that the organic light emitting element and the desiccant film face each other. And a third step of bonding by forming the organic light-emitting device.   The method of manufacturing an organic light-emitting device according to claim 1, wherein the first region is an outer peripheral portion of the second region.   In the first step, a liquid repellent film containing a liquid repellent compound as a main material is formed in the first region of the surface of the other substrate on the closed space side using a plasma polymerization method. The manufacturing method of the organic light-emitting device of Claim 1 or 2 which provides liquid repellency by this.   4. The method according to claim 1, wherein in the third step, the sealing portion is formed by solidifying a resin material supplied between the one substrate and the other substrate. 5. Manufacturing method of organic light-emitting device.   Prior to the third step, the resin is formed by forming a resin affinity film mainly composed of a compound having affinity for the resin material in a region where the sealing portion of the other substrate is formed. The manufacturing method of the organic light-emitting device of Claim 4 which provides affinity with material.   The method for manufacturing an organic light-emitting device according to claim 4, wherein the resin material includes a gap material, and the thickness of the sealing portion is defined by the gap material.   The method of manufacturing an organic light emitting device according to claim 6, wherein the gap material is composed of particles.   The method of manufacturing an organic light emitting device according to claim 6, wherein the gap material is mainly composed of a desiccant.   In the third step, the sealing portion solidifies the first resin material including the gap material supplied between the one substrate and the other substrate, and then solidifies the first resin material. The method of manufacturing an organic light emitting device according to claim 8, wherein the second resin material not including the gap material is supplied and solidified on the opposite side of the resin material to the organic light emitting element.   In the third step, the sealing portion is separated from the desiccant film by forming the liquid repellent film in the first region of the surface of the other substrate on the closed space side. A method for manufacturing an organic light emitting device according to claim 1, wherein the organic light emitting device is formed.   The manufacturing method of the organic light-emitting device according to claim 1, wherein in the third step, the desiccant film and the light-emitting element are brought into contact with each other. The water vapor permeability (specified in JIS K 7129) when the temperature of the atmosphere is 40 ° C. is 10 [g / m ² · day · 90% RH] or less. The manufacturing method of the organic light-emitting device in any one.   An organic light-emitting device manufactured by the method for manufacturing an organic light-emitting device according to claim 1. An electronic apparatus comprising the organic light-emitting device according to claim 13.

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