JP2015230869A - Electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electronic device which is excellent in sealing performance even under a changing environment.SOLUTION: In the electronic device having a body unit on a substrate 1 sealed by a sealing material 3, the substrate 1 and the sealing material 3 are bonded in a manner to sandwich an extraction electrode 4 formed to expose from the body unit. The thickness of a junction 5 between the substrate 1 and the sealing material 3 is within the range of 0.1 to 100.0 nm. The sealing material 3 includes a gas barrier layer 32 and a support medium 31 for the gas barrier layer 32. The Young's modulus of the support medium 31 at a temperature of 25°C is within the range of 0.1-3.5 GPa.

Description

  The present invention relates to an electronic device.

Electronic devices such as organic electroluminescence (EL) elements and liquid crystal display elements are likely to be deteriorated by gas such as water and oxygen in the atmosphere, and thus high sealing performance is required.
Metal or glass sealing materials have high gas barrier properties against water, oxygen, etc., but since the sealing material is joined to the substrate of the electronic device by welding or the like, the sealing material of the electronic device exposed to high temperature and high pressure is used. Deterioration is inevitable. If an adhesive made of resin such as epoxy resin is used, bonding can be performed at normal temperature and pressure, but the resin has lower gas barrier properties than metal, glass, etc. It was difficult to prevent completely.

Therefore, after forming a thin film of metal, metal oxide, etc. with high gas barrier properties on the bonding surfaces of the encapsulant and the substrate of the electronic device, a method of bonding at room temperature by surface activation treatment has also been studied. (For example, refer to Patent Documents 1 and 2 and Non-Patent Document 1).
Further, by using a silane coupling agent having a high bonding strength as an adhesive, a molecular adhesive or the like, the adhesive layer for bonding the sealing material and the substrate is made as thin as possible, and water that enters from the bonding portion, Methods for reducing oxygen and the like have been proposed (see, for example, Patent Documents 3 to 5 and Non-Patent Documents 2 and 3).

  However, high sealing performance can be obtained by these bonding methods when the bonding surface is flat and the sealing material can be bonded to the substrate without any gap. If there are irregularities on the joint surface, a gap is generated between the sealing material and the substrate, but the gap cannot be filled with metal oxide, adhesive, etc. formed as a thin film. Etc. will be allowed to enter. In particular, in the case of electronic devices, it is necessary to form wiring electrodes for driving the electronic devices so as to be drawn out from the main unit of the electronic device, and such lead electrodes usually cause unevenness on the substrate. It is.

  In addition, the sealing material may be deformed when an external load such as an expansion or contraction of the sealing material or bending of the electronic device is applied when the temperature or humidity is changed. If the layer of the adhesive or the like is thin, it cannot cope with such deformation of the sealing material, and a new gap may occur. Therefore, there has been a problem that the sealing performance is easily changed by the environment.

JP 2007-324195 A JP 2008-207221 A JP 2013-218805 A JP 2010-254793 A International Publication No. 2011/010738 Pamphlet

Ryuichi Kondou, Tadatomo Suga, Room Temperature SiO2 wafer bonding by adhesion layer method, Proceedings of the 3rd International IEEE Workshop on low Temperature Bonding for 3D Intergration, May 22-June 23,2012 Yasunori Taga, Kei Takashima, Joining technology using gas adsorption, MATERIAL STAGE, Vol.12, No.7, 2112, p34-39 Keiji Hirai, Glass, Ceramics, New Chemical Bonding Technology for Metal Components and Resins, Application and Coating, February 2012, Vol.1, No.1, p22-27

  The present invention has been made in view of the above problems and circumstances, and a solution to the problem is to provide an electronic device having excellent sealing performance even in a changing environment.

  In order to solve the above-mentioned problems, the present inventor, in the process of examining the cause of the above-mentioned problem, the extraction electrode formed on the substrate of the electronic device causes unevenness on the surface of the substrate, so It was found that gaps are likely to occur. In order to prevent gas intrusion from the joint, it is effective to make the joint as thin as possible, but if the joint is thin, the gap cannot be filled by the joint, and new gaps may be created due to environmental changes. Prone to occur. As a result of intensive studies, the present inventor can fill the gap with the sealing material by using a highly flexible sealing material, and it is difficult to create a new gap even if the environment changes. The inventors have found that sealing performance can be obtained and have reached the present invention.

That is, the subject concerning this invention is solved by the following means.
1. An electronic device in which a main unit on a substrate is sealed with a sealing material,
The substrate and the sealing material are joined with a lead electrode formed so as to be exposed from the main unit,
The thickness of the joint between the substrate and the sealing material is in the range of 0.1 to 100.0 nm,
The sealing material comprises a gas barrier layer and a support for the gas barrier layer,
An electronic device having a Young's modulus at a temperature of 25 ° C of the support in a range of 0.1 to 3.5 GPa.

  2. 2. The electronic device according to item 1, wherein the lead electrode has a thickness in a range of 10 to 500 nm.

  3. 3. The electronic device according to item 1 or 2, wherein an elongation percentage of the gas barrier layer is in a range of 0.5 to 5.0%.

  4). The first to third aspects, wherein the bonding portion includes an activation layer obtained by subjecting each bonding surface of the substrate on which the extraction electrode is formed and the sealing material to a surface activation treatment. The electronic device as described in any one of the above.

  5. The joint includes an activation layer obtained by subjecting each of a metal layer formed on the substrate on which the extraction electrode is formed and a metal layer formed on the sealing material to surface activation treatment. 4. The electronic device according to any one of items 1 to 3, which is characterized.

  6). The electronic device according to any one of Items 1 to 3, wherein the bonding portion includes an adhesive layer using a silane coupling agent or a molecular adhesive.

By the above means of the present invention, it is possible to provide an electronic device excellent in sealing performance even under changing environments.
The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.
Since the thickness of the bonding portion between the substrate and the sealing material is as thin as 0.1 to 100.0 nm, it is presumed that gas can be prevented from entering from the bonding portion and excellent sealing performance was obtained. Is done. If the junction is thin, it is difficult to fill the unevenness that the extraction electrode causes on the surface of the substrate with the junction, and a gap is likely to occur. However, since the Young's modulus of the support of the sealing material is in the range of 0.1 to 3.5 GPa and the sealing material is highly flexible, the sealing material fills the unevenness and allows gas to enter from the gap. Therefore, it is presumed that excellent sealing performance can be exhibited.

Sectional drawing which shows schematic structure of the organic EL element for illumination which concerns on this Embodiment Sectional drawing in the P1-P1 line in FIG. Diagram showing the bending test method Sectional drawing showing a junction part when surface activation processing is used for joining Sectional drawing showing a junction part in the case of forming a metal layer before surface activation processing Front view showing an example of room temperature bonding equipment Front view showing a sealing material and a substrate bonded by pressure in a room temperature bonding apparatus Sectional drawing showing a junction part in case a silane coupling agent or molecular adhesive is used for joining Sectional drawing which shows schematic structure of the organic EL element in the case of providing a protective layer (A) Top view showing schematic structure of organic EL element for display, (B) Sectional view taken along line P2-P2 in (A) (A) Top view showing layout of simulated device manufactured in Example I, (B) Sectional view of extraction electrode in (A) Sectional drawing of the extraction electrode of the organic EL element manufactured in Example II

The electronic device of the present invention is an electronic device in which a main body unit on a substrate is sealed with a sealing material, and the extraction electrode is formed so that the substrate and the sealing material are exposed from the main body unit. And the thickness of the joint between the substrate and the sealing material is in the range of 0.1 to 100.0 nm, and the sealing material comprises a gas barrier layer and the gas barrier layer. And a Young's modulus at a temperature of 25 ° C. of the support is in the range of 0.1 to 3.5 GPa.
This feature is a technical feature common to the inventions according to claims 1 to 6.

As an embodiment of the present invention, it is preferable that the thickness of the extraction electrode is in the range of 10 to 500 nm from the viewpoint of manifesting the effect of the present invention.
Further, the elongation rate of the gas barrier layer is in the range of 0.5 to 5.0%, the gas barrier layer easily deforms following the support, and the sealing material easily fills the gap. Therefore, it is preferable.

  In addition, from the viewpoint of thinning the bonding portion between the sealing material and the substrate and bonding the sealing material and the substrate at room temperature, the bonding portion is a bonding between the substrate on which the extraction electrode is formed and the sealing material. An activation layer obtained by subjecting the surface to a surface activation treatment, or a metal layer formed on the substrate on which the extraction electrode is formed and a metal layer formed on the sealing material. It is preferable to include an activation layer obtained by subjecting each to surface activation treatment.

Hereinafter, the present invention, its components, and modes for carrying out the present invention will be described in detail.
In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

  Examples of the electronic device of the present invention include an organic EL element, a liquid crystal display element, a solar cell, and a thin film transistor. Hereinafter, as an embodiment of the electronic device of the present invention, an example of an organic EL element for illumination will be described.

FIG. 1 is a cross-sectional view showing a schematic configuration of an organic EL element 10 according to an embodiment of the present invention.
As shown in FIG. 1, the organic EL element 10 is an electronic device in which a main unit 2 formed on a substrate 1 is sealed with a sealing material 3.
On the substrate 1, a plurality of lead electrodes 4 for connecting the main unit 2 to an external device such as a power source and a control computer are formed so as to be drawn from the main unit 2.

The substrate 1 and the sealing material 3 are joined with the extraction electrode 4 interposed therebetween. From the viewpoint of suppressing the intrusion of gas from the joint 5 by making the joint 5 between the substrate 1 and the sealing material 3 as thin as possible, the thickness of the joint 5 is in the range of 0.1 to 100.0 nm.
The sealing material 3 includes a support 31 and a gas barrier layer 32. The Young's modulus of the support 31 at a temperature of 25 ° C. is in the range of 0.1 to 3.5 GPa in order to fill a gap that may be generated between the substrate 1 and the sealing material 3 by thinning the bonding portion 5.

FIG. 2 shows a cross-sectional view taken along line P1-P1 of FIG.
As shown in FIG. 2, the plurality of extraction electrodes 4 formed on the substrate 1 cause unevenness on the surface of the substrate 1. As described above, since the surface of the substrate 1 cannot be flattened by the bonding portion 5 when the thickness of the bonding portion 5 is reduced within the range of 0.1 to 100.0 nm, the sealing material 3 and the substrate 1 are bonded. Sometimes a gap may be formed in the recess between the extraction electrodes 4. However, since the sealing material 3 having the Young's modulus of the support 31 within the above range is highly flexible and easily deformed, the sealing material 3 can enter the gap during bonding as shown in FIG. Not only can the joint portion 5 be thinned to prevent gas from entering from the joint portion 5, but also the gap can be filled to prevent gas from entering from the gap, and excellent sealing performance can be obtained.

Hereinafter, the details of the configuration of the organic EL element 10 will be described.
〔substrate〕
The substrate 1 preferably has a gas barrier property in order to prevent the main unit 2 from being deteriorated. The gas barrier property of the substrate 1 is preferably a water vapor permeability of 5 × 10 ⁻³ g / m ² · day or less in an environment of a temperature of 40 ° C. and a relative humidity of 90%, preferably 5 × 10 ⁻⁴ g / more preferably m is ² · day or less, further preferably 5 × ¹⁰ below -5 ^{g /} m 2 · day.

It does not specifically limit as the board | substrate 1 provided with gas-barrier property, For example, plate shape, film-form glass, a metal, etc. can be used.
As the glass, for example, quartz glass, borosilicate glass, soda glass, non-alkali glass, or the like can be used.
As metals, aluminum (Al), gold (Au), silver (Ag), chromium (Cr), iron (Fe), nickel (Ni), cobalt (Co), copper (Cu), indium (In), tin (Sn), lead (Pb), titanium (Ti), alloys thereof, and the like can be used.

  Moreover, the board | substrate 1 may be comprised including the gas barrier layer on the resin-made support bodies. Such a substrate 1 can be formed in the same manner as the sealing material 3.

  The substrate 1 can further include a bleed-out layer on the surface of the support opposite to the surface on which the gas barrier layer is provided in order to suppress the occurrence of bleed-out. Moreover, in order to improve the adhesiveness of the board | substrate 1 and a gas barrier layer, an undercoat layer can also be provided between the board | substrate 1 and a gas barrier layer.

[Main unit]
As shown in FIG. 1, the main unit 2 includes an anode 21, a hole transport layer 22, a light emitting layer 23, an electron transport layer 24, and a cathode 25 in order from the substrate 1 side.
The hole transport layer 22 and the electron transport layer 24 are arbitrary layers provided as necessary.

The anode 21 and the cathode 25 are a pair of electrodes.
As a material of the anode 21, a metal, an alloy, an electrically conductive compound, or a mixture thereof having a work function of 4 eV or more can be used.
On the other hand, as the material of the cathode 25, a metal, an alloy, an electrically conductive compound, or a mixture thereof having a work function of 4 eV or less can be used.

  The hole transport layer 22 transports holes from the anode 21 to the light emitting layer 23. A hole injection layer may be provided between the anode 21 and the hole transport layer 22 in order to lower the driving voltage and improve the light emission luminance.

The light-emitting layer 23 is a layer that emits light by recombination of holes transported from the hole transport layer 22 and electrons transported from the electron transport layer 24.
The light emitting layer 23 may have a multilayer structure in which a plurality of light emitting layers are stacked, or may be a single light emitting layer containing a plurality of light emitting materials. Especially, it is preferable that the light emitting layer 23 contains a host compound (also referred to as a light emitting host) and a light emitting material (also referred to as a light emitting dopant) and emits light with the light emitting material.

  The electron transport layer 24 transports electrons from the cathode 25 to the light emitting layer 23. An electron injection layer may be provided between the cathode 25 and the electron transport layer 24 in order to lower the drive voltage and improve the light emission luminance.

(Encapsulant)
The sealing material 3 includes a support 31 and a gas barrier layer 32 formed on the support 31.

[Support]
As described above, the support 31 has a Young's modulus at a temperature of 25 ° C. in the range of 0.1 to 3.5 GPa.
If the Young's modulus of the support 31 is within the above range, even if the joint 5 between the substrate 1 and the sealing material 3 is thin, it is sufficient to fill the gap generated in the joint 5 by the extraction electrode 4 on the substrate 1. Flexibility can be imparted to the sealing material 3.
The Young's modulus of the support 31 refers to the tensile elastic modulus defined in ASTM-D-882 and JIS-7127.

  Although it does not specifically limit as a material of the support body 31, The resin in which the Young's modulus in the temperature of 25 degreeC exists in the range of 0.1-3.5 GPa can be used preferably. Specifically, polystyrene (abbreviation: PS, Young's modulus: 2.8 to 3.5 GPa), high density polyethylene (abbreviation: HDPE, Young's modulus: 0.4 to 1.1 GPa), low density polyethylene (abbreviation: LDPE). , Young's modulus: 0.11-1.40 GPa), polypropylene (abbreviation: PP, Young's modulus: 1.1-1.4 GPa), polycarbonate (abbreviation: PC, Young's modulus: 2.5-3.5 GPa), poly Tetrafluoroethylene (abbreviation: PTFE, Young's modulus: 0.41 GPa), cycloolefin polymer (abbreviation: COP, Young's modulus: 2.2 GPa), cycloolefin copolymer (abbreviation: COC, Young's modulus: 2.5-3.2 GPa) ) Etc. can be used as the material of the support 31.

  Even when the Young's modulus of the resin itself as the material is not within the range of 0.1 to 3.5 GPa, the resin film is formed depending on the film formation conditions when the support 31 is manufactured and stretched after the film formation. And when manufacturing the support body 31, the Young's modulus of the support body 31 obtained may change also with extending | stretching conditions. Therefore, the Young's modulus of the support 31 can be set within the range of 0.1 to 3.5 GPa by adjusting the film forming conditions or the stretching conditions of the support 31.

  The thickness of the support 31 is preferably 50 μm or less because the sealing material 3 is easily deformed and the gap is easily filled, and more preferably 30 μm or less.

[Gas barrier layer]
The gas barrier layer 32 is provided to prevent permeation of gases such as oxygen and water in the atmosphere.
The material of the gas barrier layer 32 is not particularly limited. For example, silicon (Si), aluminum (Al), indium (In), tin (Sn), zinc (Zn), titanium (Ti), copper (Cu), Metals such as cerium (Ce) and tantalum (Ta), and metal compounds such as oxides, nitrides, carbides, oxynitrides, and oxide carbides of these metals can be used.

  Specific examples of the metal compound include silicon oxide, aluminum oxide, titanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), tantalum oxide, zirconium oxide, niobium oxide, aluminum silicate, boron carbide, tungsten carbide, Silicon carbide, silicon oxycarbide, aluminum nitride, silicon nitride, boron nitride, aluminum oxynitride, silicon oxynitride, boron oxynitride, zirconium oxide boride, titanium oxide boride, metal oxide boride, diamond-like carbon (abbreviation: DLC) ) And the like. Among these, indium tin oxide, silicon oxide, aluminum oxide, aluminum silicate, silicon nitride, or silicon oxynitride is preferable because of its high gas barrier property. Note that indium tin oxide is an example of a special material that can be conductive.

The method for forming the gas barrier layer 32 using the above metal or metal compound is not particularly limited, for example, sputtering methods such as magnetron cathode sputtering, flat plate magnetron sputtering, double pole AC flat plate magnetron sputtering, double pole AC rotating magnetron sputtering, resistance, etc. Heat deposition, electron beam deposition, ion beam deposition, plasma enhanced (PE) deposition, thermal CVD (Chemical Vapor Deposition), catalytic chemical vapor deposition, capacitively coupled plasma CVD , Photo CVD method, PECVD method, epitaxial growth method, atomic layer growth method, reactive sputtering method and the like.
Further, a metal layer may be formed as the gas barrier layer 32 by performing metal plating on the surface of the support 31 or by bonding a metal foil to the support 31.

The elongation of the gas barrier layer 32 is more preferably in the range of 0.5 to 5.0%.
If the elongation is 0.5% or more, the gas barrier layer 32 easily deforms following the support 31 having a Young's modulus in the range of 0.1 to 3.5 GPa, and the sealing material 3 has a gap. It becomes easier to fill. Moreover, if the elongation is 5.0% or less, high gas barrier properties can be maintained.

The elongation percentage of the gas barrier layer 32 can be measured as follows.
As shown in FIG. 3, the sealing material 3 is bent and fixed by being sandwiched between two parallel plates 70 and stored at room temperature (25 ° C.) for 24 hours. The sealing material 3 is curved so that the gas barrier layer 32 is located outside. Thereafter, the curved portion is observed with a microscope at the same room temperature to check whether cracks are generated. If no crack has occurred, the same operation is repeated with the distance d between the two plates 70 smaller than the previous time. If a crack occurs, the distance d between the two plates 70 at the time of the operation immediately before the occurrence of the crack and the thickness of the support 31 of the sealing material 3 are used to calculate the curved portion of the gas barrier layer 32 according to the following formula. A curvature radius r is obtained.
Radius of curvature r = (distance d−thickness of support) / 2
From the calculated radius of curvature r, the elongation percentage (%) of the gas barrier layer 32 is determined by the following formula.
Elongation rate (%) = (thickness of support / 2r) × 100

The gas barrier layer 32 having an elongation percentage in the range of 0.5 to 5.0% can be obtained by adjusting the atomic composition of the gas barrier layer 32.
For example, when the main component of the gas barrier layer 32 is silicon oxide, the elongation can be adjusted within a range of 0.5 to 5.0% by further introducing carbon atoms and metal atoms.
Specifically, when the structure of silicon oxide into which carbon atoms and metal atoms are introduced is represented by the general formula SiO _x C _w M _z , the atomic composition ratio w of carbon atoms C to be introduced is 0. When the atomic composition ratio z of the metal atom M to be introduced is within the range of 0.05 to 0.25, the elongation is within the range of 0.5 to 5.0%. The gas barrier layer 32 can be obtained.

  The metal atom M that can be introduced into silicon oxide is not particularly limited as long as it is an element belonging to Group 13 of the long-period periodic table. However, boron, aluminum, gallium, or indium is preferable, and aluminum is easy in terms of easy adjustment of elongation. Is preferred. Group 13 elements such as boron, aluminum, gallium, and indium have a trivalent valence, and since the valence is insufficient compared to the tetravalent valence of silicon, the flexibility of the film is increased. It becomes possible to adjust the elongation rate to 0.5% or more.

Further, when the main component of the gas barrier layer 32 is silicon nitride or silicon oxynitride, the elongation can be adjusted within a range of 0.5 to 5.0% by further introducing hydrogen atoms.
Specifically, when the structures of silicon nitride and silicon oxynitride into which hydrogen atoms are introduced are represented by general formulas SiN _y H _v and SiO _x N _y H _v , respectively, When the atomic composition ratio v is in the range of 0.2 to 1.0, the gas barrier layer 32 having an elongation percentage in the range of 0.5 to 5.0% is obtained.
When silicon oxynitride is used as the main component of the gas barrier layer 32, 2x + 3y <3.5 is particularly preferable, but 2.0 <2x + 3y is preferable from the viewpoint of improving the gas barrier property.

The atomic composition ratio of the gas barrier layer 32 can be adjusted by adjusting the supply ratio of the raw materials when the gas barrier layer 32 is formed.
For example, when the gas barrier layer 32 containing a silicon compound is formed by PECVD, an organic silicon compound containing silicon can be used as a source gas supplied to a discharge region where plasma is generated. Specific examples of organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), hexamethylsilazane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, and methyltrimethylsilane. , Hexamethyldisilane, silane, methylsilane, dimethylsilane, trimethylsilane, tetramethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) ) And the like. Since these organosilicon compounds have an alkyl group or the like, hydrogen atoms can be introduced into the silicon compound. The atomic composition ratio v of hydrogen atoms can be adjusted by the supply amount of the organosilicon compound and the supply amount of an oxidizing agent such as oxygen.

In the case of oxidizing the organosilicon compound, oxygen, ozone or the like may be further supplied, and in the case of nitriding, nitrogen, ammonia or the like may be further supplied. When ammonia is used, a hydrogen atom can be introduced into the silicon compound.
When carbon atoms are introduced into the silicon compound, methane, ethane, ethylene, acetylene, etc. can be further supplied as a raw material gas.

The atomic composition ratios x, y, z, and w in the gas barrier layer 32 can be obtained by combining the analysis by X-ray photoelectron spectroscopy (XPS) and rare gas ion sputtering such as argon. It can be confirmed by a so-called depth profile measurement in which surface composition analysis is sequentially performed while exposing. Specific analysis conditions are as follows.
(Analysis conditions)
Analyzer: QUANTERASXM (manufactured by ULVAC-PHI)
X-ray source: Monochromatic Al-α
Measurement area: Si2p, C1s, N1s, O1s, M *
(M * represents the optimum measurement region depending on the metal. For example, B1s for boron, Al2p for aluminum, Ga3d or Ga2p for gallium, In3d for indium, (In the case of thallium, it is Tl4f.)
Sputter ion: Ar (2 keV)
Depth profile: After sputtering for 1 minute, repeat the measurement operation and determine the composition by the average value in the thickness direction of the gas barrier layer. Quantification: Obtain the background by the Shirley method, and calculate the relative sensitivity coefficient method from the obtained peak area. Data processing: MultiPak (manufactured by ULVAC-PHI)
In addition, since the surface adsorbed water, organic matter contamination, etc. may affect the analysis result, it is preferable to discard the first measurement result.

Further, the surface roughness Ra of the gas barrier layer 32 is preferably 3 nm or less. The surface roughness Ra is an arithmetic average roughness defined in JIS B0601 (2001).
Since the bonding strength increases as the bonding surface with the substrate 1 becomes flat, the bonding strength can be increased by setting the surface roughness Ra of the gas barrier layer 32 to 3 nm or less.
The surface roughness Ra of the gas barrier layer 32 depends on the unevenness of the support 31, the material of the gas barrier layer 32, the formation method, and the like. In general, since the film formation rate is low and a film in which the temperature during film formation is high is easily obtained, the surface roughness Ra is set to 3 nm or less by adjusting the film formation conditions of the gas barrier layer 32. can do.

  The thickness of the gas barrier layer 32 is preferably in the range of 3 to 1000 nm, more preferably in the range of 10 to 500 nm, from the viewpoint of exhibiting high gas barrier properties without impairing the flexibility of the support 31. preferable.

The gas barrier layer 32 may be a layer formed by applying a coating liquid containing an inorganic precursor such as polysilazane on the support 31 and then performing a modification treatment.
Polysilazane is a polymer having a silicon-nitrogen bond. A commercially available polysilazane solution dissolved in an organic solvent can also be used for the gas barrier layer 32. Examples of commercially available products include NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials Co., Ltd. .

  When the metal atom M is introduced into the polysilazane coating film after the modification treatment in order to adjust the elongation within the range of 0.5 to 5.0%, a metal compound may be mixed in the polysilazane solution. . The metal compound is preferably a metal alkoxide because efficient film formation is possible. Examples of the metal alkoxide that can be used include trimethyl borate, aluminum trimethoxide, aluminum acetylacetonate, acetoalkoxyaluminum diisopropylate, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, gallium methoxide, gallium acetylacetonate, Examples include tris (2,4-pentanedionato) indium, indium isopropoxide, indium methoxyethoxide, thallium ethoxide, thallium acetylacetonate, and the like.

The gas barrier layer 32 may be a laminate of an inorganic layer containing the metal or metal compound and an organic layer containing an organic polymer.
The organic layer is formed by, for example, applying an organic monomer or organic oligomer on the support 31 and then polymerizing using an electron beam device, a UV light source, a discharge device or the like, or cross-linking as necessary. Can do. The organic layer can also be formed by depositing an organic monomer or organic oligomer capable of flash evaporation or radiation crosslinking on the support 31 and then forming a polymer from the organic monomer or organic oligomer. Examples of the coating method of the organic monomer or organic oligomer include a roll coating method such as a gravure roll coating method and a spray coating method such as an electrostatic spray method. The coating efficiency can be improved by cooling the support 31. Moreover, as an example of the laminated body of an inorganic layer and an organic layer, the laminated body described in international publication 2012/003198, international publication 2011/013341, etc. is mentioned.

  In the case of a laminate of an inorganic layer and an organic layer, the thickness of each layer may be the same or different. The thickness of the inorganic layer is preferably in the range of 3 to 1000 nm, and more preferably in the range of 10 to 300 nm. The thickness of the organic layer is preferably in the range of 100 nm to 100 μm, and more preferably in the range of 300 nm to 50 μm.

[Extraction electrode]
As shown in FIG. 1, the extraction electrode 4 is formed so as to be exposed from the anode 21 and the cathode 25 of the main unit 2 to the end of the substrate 1.

Examples of the extraction electrode 4 include indium tin oxide (ITO), aluminum-doped zinc oxide (AZO), fluorine-doped tin oxide (FTO), tin oxide (SnO ₂ ), zinc oxide (ZnO), and titanium oxide (TiO ₂ ). Transparent metal oxides, metals such as Ag, Al, Au, Pt, Cu, Rh, In, Ni, Pd, and Mo, metal nanowires, carbon nanotubes, and nanoparticles can be used. The lead electrode 4 may have a structure in which two or more kinds of metals are laminated, or may be formed of the same material as the anode 21 or the cathode 25.

  The thickness of the extraction electrode 4 is preferably in the range of 10 to 500 nm from the viewpoint of increasing conductivity.

(Joint part)
The joint portion 5 is a joint portion between the substrate 1 and the sealing material 3. As described above, the thickness of the bonding portion 5 is 0.1 to 100.0 nm from the viewpoint of making the bonding portion 5 between the substrate 1 and the sealing material 3 as thin as possible to prevent gas from entering from the bonding portion 5. Is in range.

As a bonding method of the substrate 1 and the sealing material 3, the thickness of the bonding portion 5 is thinned within a range of 0.1 to 100.0 nm to obtain a high bonding strength that is difficult to peel off even if the bonding portion 5 is thin. In addition, in order to prevent deterioration of the main body unit 2 and the like due to high energy such as high heat and high pressure, the bonding surfaces of the substrate 1 on which the extraction electrode 4 is formed and the sealing material 3 are subjected to surface activation treatment and then pressurized and bonded. The method is preferably used.
The surface activation treatment is a treatment for chemically activating by changing the hydrophilicity, hydrophobicity, roughness, etc. of the surface, and examples thereof include corona treatment, plasma treatment, ozone treatment, electromagnetic wave irradiation treatment and the like.
In the case of this bonding method, as shown in FIG. 4, the bonding portion 5 includes an activation layer 511 obtained by surface activation treatment of the bonding surface of the substrate 1 on which the extraction electrode 4 is formed, and the sealing material 3. And an activation layer 512 obtained by surface activation treatment of the bonding surface.

Depending on the material of the bonding surface, in order to increase the bonding strength, a metal layer is formed on each bonding surface of the substrate 1 and the sealing material 3 on which the extraction electrode 4 is formed, and the metal layer is subjected to surface activation treatment before being applied. A pressure bonding method can also be used.
In the case of this bonding method, as shown in FIG. 5, the bonding portion 5 was obtained by forming a metal layer on the substrate 1 on which the extraction electrode 4 was formed and then surface-activating the metal layer. An activation layer 521 and an activation layer 522 obtained by forming a metal layer on the sealing material 3 and then surface-activating the metal layer are included.

Examples of the metal that can be used for forming the metal layer include Si, Ti, Pt, Cr, Fe, Ni, Ag, and Au. From the viewpoint of increasing the bonding strength, an alloy of Si and Fe or an alloy of Al and Fe is preferable.
As a method for forming the metal layer, a CVD method can be used in addition to a PVD method such as a sputtering method or an ion plating method.

FIG. 6 shows an example of a room temperature bonding apparatus that can be used for the above-described room temperature bonding.
As shown in FIG. 6, the room temperature bonding apparatus 100 includes an ion gun 102, a metal target T1 holder 103, a metal target T2 holder 104, a substrate 1 holder 105, and a sealing member in a vacuum chamber 101 adjusted under a vacuum pressure. A holder 106 for the material 3 is provided.

The ion gun 102 irradiates an ion beam toward the metal targets T1 and T2 fixed to the holders 103 and 104, respectively, and sputters the metal targets T1 and T2. The components of the metal targets T1 and T2 are deposited on the substrate 1 and the sealing material 3 by the sputter, and a metal layer is formed.
In order to form the metal layer at the bonding margin between the substrate 1 and the sealing material 3, a mask that covers a region other than the bonding margin may be used. The joining margin refers to a region where the substrate 1 and the sealing material 3 are joined.

  The ion gun 102 irradiates an ion beam toward the substrate 1 and the sealing material 3 fixed to the holders 105 and 106, respectively, for the purpose of surface activation treatment or cleaning treatment of the substrate 1 and the sealing material 3. Reverse sputtering can also be performed.

  The holder 105 of the substrate 1 and the holder 106 of the sealing material 3 are arranged so that the substrate 1 and the sealing material 3 face each other in the vertical direction, and can move in the vertical direction. By bringing the holders 105 and 106 close to each other, the substrate 1 and the sealing material 3 can be brought into contact with each other and pressed to bond the substrate 1 and the sealing material 3.

A processing procedure at the time of bonding using the room temperature bonding apparatus 100 will be described.
First, a mask that covers a region other than the bonding margin is arranged on the substrate 1 and the sealing material 3, and the arrangement positions of the substrate 1 and the sealing material 3 are adjusted so that the positions of the respective bonding margins coincide with each other. If necessary, the ion gun 102 irradiates the substrate 1 and the sealing material 3 with an ion beam and performs reverse sputtering to perform a surface activation process or a cleaning process. Thereafter, the metal targets T 1 and T 2 are irradiated with an ion beam by the ion gun 102 to form a metal layer on the substrate 1 and the sealing material 3. When a metal layer having a desired thickness is obtained, the ion gun 102 again irradiates the substrate 1 and the sealing material 3 with an ion beam to subject the metal layer to surface activation treatment. After removing the mask, as shown in FIG. 7, the holder 106 is lowered and the holder 105 is raised to join the sealing material 3 fixed to the holder 106 and the substrate 1 fixed to the holder 105. Join.

In addition to the above-described bonding method, a main unit with high energy such as high heat and high pressure is obtained in order to obtain a high bonding strength that is difficult to peel off even if the thickness of the bonding portion 5 is in the range of 0.1 to 100.0 nm. In order to prevent the degradation of 2 and the like, a bonding method in which a silane coupling agent or a molecular adhesive is applied to one or both bonding surfaces of the substrate 1 and the sealing material 3 to form an adhesive layer, and the adhesive layers are bonded together Can also be used.
Depending on the materials of the substrate 1 and the sealing material 3, the surface of each of the substrate 1 and the sealing material 3 is subjected to surface activation treatment, and then an adhesive is applied.
In the case of this bonding method, as shown in FIG. 8, the bonding portion 5 includes an activation layer 531 a obtained by surface-activating the bonding surface of the substrate 1 on which the extraction electrode 4 is formed, and the activation layer. An adhesive layer 531b obtained by applying a silane coupling agent or a molecular adhesive on 531a, an activation layer 532a obtained by subjecting the bonding surface of the sealing material 3 to surface activation, and the activation layer And an adhesive layer 532b obtained by applying a silane coupling agent or a molecular adhesive on 532a.

  The silane coupling agent that can be used is not particularly limited. For example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- ( 1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane , 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and the like.

Moreover, as a molecular adhesive which can be used, the compound which has a structure represented, for example by following General formula (1) is mentioned.
R ₁ —R ₂ —SiX ¹ _(3-n) Y ¹ _n (1)
[Wherein R ₁ represents a reactive functional group containing at least one of carbon, hydrogen, oxygen, nitrogen, and sulfur. R ₂ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group, and a hetero atom or a functional group may intervene in these substituents. X ¹ represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group, a halogen atom or a hydrogen atom, Y ¹ represents an alkyloxy group having 1 to 10 carbon atoms, and n is 1, 2 or 3 is represented. ]

Here, as is apparent from the structure of the general formula (1), the molecular adhesive is a group that can be chemically bonded to the substrate surface having an OH group (alkoxysilyl group, Y ¹ in the general formula (1)). And a group capable of reacting with the resin (reactive group, R ₁ in the general formula (1)) is contained in one molecule. By chemically bonding such a molecular adhesive to the surface of the substrate 1 or the sealing material 3, a reactive solid surface having excellent reactivity can be obtained.

  Specific examples of the molecular adhesive represented by the general formula (1) include amines such as 3-aminopropyltriethoxysilane and 3- (3-aminopropoxy) -3,3-dimethyl-1-propenyltrimethoxysilane. Materials, vinyl materials such as vinyltrimethoxysilane and vinyltriethoxysilane, epoxy materials such as 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane and the like.

[Protective layer]
The organic EL element 10 can include a protective layer 6 as shown in FIG. 9 as necessary from the viewpoint of preventing damage due to bonding of the substrate 1 and the extraction electrode 4.
The protective layer 6 may be formed so as to cover at least the extraction electrode 4 positioned at the joining margin, but is formed so as to cover the entire surface of the substrate 1 including the main unit 2 as shown in FIG. May be.
The protective layer 6 can be formed in the same manner as the gas barrier layer 32 of the sealing material 3 from the viewpoint of improving the gas barrier property and preventing the deterioration of the main unit 2.

  When the protective layer 6 is provided, the protective layer 6 on the substrate 1 is subjected to surface activation treatment for bonding, and the bonding portion 5 includes an activation layer obtained by subjecting the protective layer 6 to surface activation treatment. .

[Other Embodiments]
Although the example of the organic EL element 10 for illumination was demonstrated, this invention is applicable also to the organic EL element for displays.
FIG. 10A is a top view showing a schematic configuration of an organic EL element 10B for display. FIG. 10B is a cross-sectional view taken along line P2-P2 in FIG.
The organic EL element 10B for display is sealed in the same manner as the organic EL element 10 although the configuration and layout of the organic EL element 10 for illumination and the main unit 2 are different. Therefore, in FIG. 10 (A) and FIG. 10 (B), the same code | symbol is attached | subjected about the same component as the organic EL element 10 for illumination.

  As shown in FIGS. 10A and 10B, the organic EL element 10 </ b> B is an electronic device in which a main unit 200 formed on a substrate 1 is sealed with a sealing material 3. As the main unit 200, a pixel unit 201 and a drive circuit unit 202 are provided.

As shown in FIG. 10B, the pixel portion 201 is provided with a switching TFT (Thin Film Transistor) 301, a current control TFT 302, and a light emitting element 303. The light-emitting element 303 includes a pair of electrodes 305 and an electroluminescent layer 306 sandwiched between the pair of electrodes 305. One of the pair of electrodes 305 is formed using a metal compound such as Ti, TiSi _x N _y , WSi _x , WN _x , WSi _x N _y , NbN, or ITO, and the other is a metal such as MgAg, AlLi, or CaF _2. It can be formed using a compound. The electroluminescent layer 306 can be formed by laminating Alq ₃ doped with Nile Red, TPD (aromatic diamine) or the like by a vapor deposition method, or by applying a polyvinyl carbazole (PVK) solution by a coating method. It can also be formed.

The driver circuit portion 202 is configured by a CMOS circuit in which an n-channel TFT 401 and a p-channel TFT 402 are combined.
An insulating layer 304 is provided on the substrate 1 and on the THTs 301, 302, 401 and 402. As the insulating layer 304, an organic material such as polyimide can be used in addition to an inorganic material such as a silicon compound.

As shown in FIGS. 10A and 10B, on the substrate 1, an extraction electrode 4 for transmitting a control signal from the outside is extracted from each of the pixel portion 201 and the drive circuit portion 202. It is formed in this way. The extraction electrode 4 and the main unit 200 may be covered with a protective layer.
Further, the substrate 1 and the sealing material 3 are joined with the extraction electrode 4 interposed therebetween as shown in FIG.

  Similarly to the organic EL element 10, in the organic EL element 10B, since the thickness of the bonding portion 5 is in the range of 0.1 to 100.0 nm, the bonding portion 5 between the substrate 1 and the sealing material 3 is made as thin as possible. Thus, gas intrusion from the joint 5 can be suppressed. Further, since the Young's modulus of the support 31 of the sealing material 3 is in the range of 0.1 to 3.5 GPa, the sealing material 3 can fill a gap generated by the extraction electrode 4, and sealing performance can be improved. Can be increased.

  As described above, the present invention can be applied to any organic EL element in which the substrate and the sealing material are bonded with the extraction electrode interposed therebetween, regardless of whether it is for illumination or display. Similarly, the present invention can be applied not only to organic EL elements but also to other electronic devices such as solar cells as long as the electronic device has a substrate and a sealing material bonded to each other with an extraction electrode interposed therebetween. it can.

[Method for producing organic EL element]
As an example of the method for manufacturing an electronic device of the present invention, a method for manufacturing the organic EL element 10 will be described.
The organic EL element 10 includes (1) a step of forming the main body unit 2 on the substrate 1, (2) a step of forming the extraction electrode 4, and (3) a step of bonding the substrate 1 and the sealing material 3. And including.
Hereinafter, the detail of each process (1)-(3) is demonstrated.

(1) Step of Forming Main Unit 2 First, an anode 21, a hole transport layer 22, a light emitting layer 23, an electron transport layer 24, and a cathode 25 are sequentially formed on the substrate 1.
As a method for forming the anode 21 and the cathode 25, an evaporation method, a sputtering method, or the like can be used.
The hole transport layer 22, the light emitting layer 23, and the electron transport layer 24 can be formed by a spin coating method, a casting method, an LB method, an ink jet method, a vacuum deposition method, or the like. Among these, the vacuum deposition method or the spin coating method is preferable because a homogeneous film is easily obtained and pinholes are hardly generated.

(2) Step of Forming Lead Electrode 4 Next, the lead electrode 4 exposed from the anode 21 and the cathode 25 to the edge of the substrate 1 is formed.
As a method for forming the extraction electrode 4, the same vapor deposition method, sputtering method, or the like as the anode 21 and the cathode 25 can be used. When the extraction electrode 4 is formed in parallel with the anode 21 and the cathode 25 using the same material as the material of the anode 21 and the cathode 25, the extraction electrode 4 of the wiring pattern may be formed using a mask. In order to obtain a desired shape, the extraction electrode 4 may be formed using a photolithography method.

(3) The process of joining the board | substrate 1 and the sealing material 3 After forming the extraction electrode 4, the board | substrate 1 and the sealing material 3 are joined.
As a bonding method, as described above, the thickness of the bonding portion 5 can be reduced within a range of 0.1 to 100.0 nm. It is preferable.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless there is particular notice, it represents "mass part" or "mass%".

<Example I>
[Encapsulant 1]
A 50 μm-thick polyethylene terephthalate (abbreviation: PET) film KEL86W-50 μm (manufactured by Teijin Ltd.) was prepared as a support. The Young's modulus of this PET film was measured at 25 ° C. in accordance with ASTM-D-882 and JIS-7127, and found to be 4.2 GPa. Specifically, the sample of the PET film was pulled at a speed of 50 mm / min using a tensile tester, and the maximum elasticity immediately before the sample was deformed, that is, the tangent of the maximum slope of the SS curve was obtained.

The support was subjected to a surface activation treatment by corona discharge. Further, propylene glycol monomethyl ethanol (PGME) was added to UV curable resin OPSTAR Z7527 (manufactured by JSR) to prepare a coating solution so that the solid content concentration was 30% by mass. This coating solution was applied to the surface of the support that had been surface-activated by an extrusion coater so that the film thickness after drying was 2 μm. The coating film was dried at a temperature of 80 ° C. for 3 minutes and then cured by irradiating with an ultraviolet light with an integrated light quantity of 0.5 J / cm ^{2 with} a high-pressure mercury lamp to form an undercoat layer.
On the support on which the undercoat layer was formed, a gas barrier layer of type 01 was formed by the following procedure to produce a sealing material 1.

[Type 01 gas barrier layer]
In a film formation apparatus using a PECVD method, a mixed gas of hexamethyldisiloxane (HMDSO) and oxygen gas was supplied into the chamber. Thereafter, the support was transported to a discharge region where plasma was generated by applying a voltage, and a gas barrier layer having a thickness of 80 nm was formed on the undercoat layer of the support.

Specific film forming conditions are as follows.
(Deposition conditions)
Source gas mixing ratio: hexamethyldisiloxane / oxygen = 100/1000 (unit of supply amount of each source gas is sccm; standard cubic centimeter per minute)
Degree of vacuum: 1.5Pa
Power supply for plasma generation power supply: 1 kW
Frequency of power source for plasma generation: 80 kHz
Support conveyance speed: 5 m / min

Using a film permeability evaluation apparatus API-BA90 (manufactured by Japan API Co., Ltd.), the water vapor transmission rate of the sealing material 1 at a temperature of 40 ° C. and a relative humidity of 90% was measured, and 7.0 × 10 ⁻⁵ g / m. ² · day.

When the elongation percentage of the gas barrier layer of the sealing material 1 was measured by the following procedure, it was 1.7%.
As shown in FIG. 3, the sealing material is curved and sandwiched between two parallel plates 70 so that the gas barrier layer of the sealing material is located outside, and is fixed at room temperature (25 ° C.). For 24 hours. Then, the curved part was observed with the microscope under the same room temperature, and it was confirmed whether the crack has generate | occur | produced. If no crack was generated, the same operation was repeated with the distance d between the two plates 70 made smaller than the previous time. When a crack occurs, the curvature radius r of the curved portion of the gas barrier layer is calculated from the distance d between the two plates at the time of operation immediately before the crack does not occur and the thickness of the support of the sealing material by the following formula. Asked.
Radius of curvature r = (distance d−thickness of support) / 2
From the calculated radius of curvature r, the elongation of the gas barrier layer was determined by the following formula.
Elongation rate (%) = (thickness of support / 2r) × 100

  Further, when the surface roughness Ra of the 10 μm × 10 μm gas barrier layer was measured using an atomic force microscope (AFM) according to JIS B0601: 2001, it was 1.1 nm.

[Sealant 2-11]
In the production of the encapsulant 1, each encapsulant 2 to 11 is the same as the encapsulant 1 except that the support of the encapsulant 1 is changed to a resin film having the following Young's modulus and thickness. Manufactured.
Sealing material 2: ZEONOR film (registered trademark) ZF-14, cycloolefin polymer (abbreviation: COP) film manufactured by Nippon Zeon Co., Ltd., Young's modulus 2.20 GPa, thickness 50 μm
Sealing material 3: Upilex (registered trademark) 50S, polyimide (abbreviation: PI) film manufactured by Ube Industries, Young's modulus 9.20 GPa, thickness 50 μm
Sealing material 4: Pure Ace (registered trademark) WR-W, Teijin's polycarbonate (abbreviation: PC) film, Young's modulus 3.50 GPa, thickness 50 μm
Sealing material 5: LL linear low density polyethylene film LL-XHT, low density polyethylene (abbreviation: LDPE) film manufactured by Futamura Chemical Co., Young's modulus 0.70 GPa, thickness 50 μm
Sealing material 6: unstretched polypropylene film FG-LTH, non-stretched polypropylene (abbreviation: CPP) film manufactured by Futamura Chemical Co., Young's modulus 1.1 GPa, thickness 50 μm
Sealing material 7: Moretec (registered trademark) film 0258CN, a low-density polyethylene (abbreviation: LDPE) film manufactured by Prime Polymer Co., Ltd., Young's modulus 0.35 GPa, thickness 50 μm
Sealing material 8: Moretech (registered trademark) film 0218CN, low-density polyethylene (abbreviation: LDPE) film manufactured by Prime Polymer, Young's modulus 0.11 GPa, thickness 50 μm
Sealing material 9: LUMITAC (registered trademark) film 43-1; low-density polyethylene (abbreviation: LDPE) film manufactured by Tosoh Corporation, Young's modulus 0.08 GPa, thickness 50 μm
Sealing material 10: LL linear low-density polyethylene film LL-XHT, a low density polyethylene (abbreviation: LDPE) film manufactured by Futamura, Young's modulus 0.70 GPa, thickness 20 μm
Sealing material 11: ZEONOR film (registered trademark) ZF-14, cycloolefin polymer (abbreviation: COP) film manufactured by Nippon Zeon Co., Ltd., Young's modulus 2.20 GPa, thickness 25 μm

The gas barrier properties of the respective sealing materials 2 to 11 were measured in the same manner as the sealing material 1, and the measurement results shown in Table 1 and Table 2 below were obtained.
The elongation rate and surface roughness Ra of the gas barrier layers of the respective sealing materials 2 to 11 were the same as those of the sealing material 1.

[Encapsulant 12]
In the production of the encapsulant 4, the encapsulant 12 was produced in the same manner as the encapsulant 4 except that instead of the type 01 gas barrier layer, a type 02 gas barrier layer was formed by the following procedure. . The type 02 gas barrier layer has a two-layer structure.

[Method for forming type 02 gas barrier layer]
First, in a film formation apparatus using a PECVD method, a mixed gas of hexamethyldisiloxane (HMDSO) and oxygen gas was supplied into a chamber. Thereafter, the support was transported to a discharge region where a voltage was applied to generate plasma, and a first gas barrier layer was formed on the undercoat layer of the support. The thickness of the first gas barrier layer was 80 nm.

The specific film forming conditions for the first gas barrier layer are as follows.
(Deposition conditions)
Gas mixing ratio: hexamethyldisiloxane / oxygen = 100/1000 (unit of supply amount of each source gas is sccm)
Degree of vacuum: 1.5Pa
Power supply for plasma generation power supply: 1 kW
Frequency of power source for plasma generation: 80 kHz
Support conveyance speed: 5 m / min

Dibutyl ether solution NAX120-20 containing 1% by mass of N, N, N ′, N′-tetramethyl-1,6-diaminohexane and 19% by mass of perhydropolysilazane as an amine catalyst (manufactured by AZ Electronic Materials Co., Ltd.) ) Was added to 0.5 g of aluminum ethyl acetoacetate diisopropylate, stirred at 80 ° C. for 1 hour, and allowed to cool to prepare a coating solution for the second gas barrier layer.
In the atmosphere at a temperature of 23 ° C. and a relative humidity of 50% RH, the prepared coating liquid for the second gas barrier layer is applied on the first gas barrier layer so that the dry film thickness becomes 150 nm. It applied by the extrusion method. After drying at room temperature for 10 minutes, under a nitrogen atmosphere in which the oxygen concentration was adjusted within a range of 0.01 to 0.10% by volume, irradiation with vacuum ultraviolet rays having a wavelength of 172 nm and an integrated light amount of ² J / cm ² was performed at 80 ° C. A second gas barrier layer was formed.

When the gas barrier property of the sealing material 12 was measured in the same manner as that of the sealing material 1, it was 6.0 × 10 ⁻⁵ g / m ² · day.
Moreover, when the elongation rate and surface roughness Ra of the sealing material 12 were measured like the sealing material 1, the elongation rate was 2.5% and surface roughness Ra was 0.8 nm.

[Encapsulant 13]
In the production of the encapsulant 4, the encapsulant 13 was produced in the same manner as the encapsulant 4 except that a type 03 gas barrier layer was formed by the following procedure instead of the type 01 gas barrier layer. . The type 03 gas barrier layer is a laminate of an inorganic layer and an organic layer.

[Type 03 gas barrier layer]
In the same manner as in Example 1 of International Publication 2012/003198, the pressure in the chamber was reduced to 0.0013 Pa, plasma was generated at an output of 0.05 kW, and the surface of the support was subjected to nitrogen plasma treatment. Next, SRS-833S (tricyclodecane dimethanol diacrylate) vacuum degassed at a pressure of 2.7 Pa was ejected at a flow rate of 1.0 mL / min with an ultrasonic sprayer operating at a frequency of 60 kHz, It was applied to the surface. At this time, a nitrogen gas flow heated to 100 ° C. at a flow rate of 10 cm ³ / min was intensively added to SRS-833S in an ultrasonic atomizer. Into a chamber maintained at 260 ° C., SRS-833S and a gas mixture were introduced, along with additional 25 sccm of heated nitrogen gas, and the resulting monomer vapor stream was condensed on the support surface. Further, an 800 nm acrylate layer was formed by irradiating with an electron beam using a multifilament electron beam curing gun operated at 9.0 kV and 3.1 mA and crosslinking.

  After forming the acrylate layer, silicon and aluminum were sputtered to form an oxide layer of silicon and aluminum having a thickness of 30 nm on the acrylate layer. Specifically, a target containing silicon and aluminum at a content ratio of 90% and 10%, respectively, was sputtered with a gas mixture containing 850 sccm of argon and 82 sccm of oxygen. The sputter pressure was 0.5 Pa, and the power used during sputtering was 3500 W.

  The operation of forming the acrylate layer and the silicon and aluminum oxide layer is repeated three times, and acrylate layer / silicon and aluminum oxide layer / acrylate layer / silicon and aluminum oxide layer / acrylate layer / silicon and aluminum oxidation A gas barrier layer having a layered structure of physical layers was formed.

It was 6.0 * 10 < ^-5 > g / m < ² > * day when the gas barrier property of the sealing material 13 was measured similarly to the sealing material 1. FIG.
Moreover, when the elongation rate and surface roughness Ra of the sealing material 13 were measured like the sealing material 1, the elongation rate was 1.3% and surface roughness Ra was 1.2 nm.

[Sealing materials 14 and 15]
In the production of the encapsulant 12, each encapsulant 14 and 15 is the same as the encapsulant 12 except that the support of the encapsulant 12 is changed to a resin film having the following Young's modulus and thickness. Manufactured.
Sealing material 14: Moretec (registered trademark) film V-0398CN, low density polyethylene (abbreviation: LDPE) film manufactured by Prime Polymer Co., Ltd., Young's modulus 0.10 GPa, thickness 50 μm
Sealing material 15: Pure Ace (registered trademark) WR, Teijin's polycarbonate (abbreviation: PC) film, Young's modulus 3.60 GPa, thickness 50 μm
The gas barrier properties of the sealing materials 14 and 15, the elongation rate of the gas barrier layer, and the surface roughness Ra were the same as those of the sealing material 12.

[Simulated device 101]
As an electronic device for testing, a simulated device 101 was manufactured using the sealing material 1 as follows.
After an aluminum film was formed on a glass substrate by a sputtering method, the aluminum film was formed into a stripe shape by a photolithography method to form 1000 lead electrodes. In addition, a magnesium layer was formed in the center of the substrate by vapor deposition instead of the main unit.
FIG. 11A shows the layout of the extraction electrode and the magnesium layer on the substrate.
As shown in FIG. 11A, the substrate 81 had a size of 50 mm × 50 mm and a thickness of 0.7 mm. The magnesium layer 83 had a size of 30 mm × 30 mm and a thickness of 100 nm. The 1000 lead electrodes 82 were formed at equal intervals at positions 5 mm away from both ends of the substrate 81. As shown in FIG. 11B, each extraction electrode 82 has a trapezoidal cross-sectional shape, a bottom width of 20 μm, and a thickness of 10 nm. Further, the spacing between the lead electrodes 82 was 20 μm, and the distance between the centers in the width direction was 40 μm.

The prepared sealing material 1 was bonded to the substrate on which the magnesium layer was formed by the following bonding method I to manufacture the simulated device 101.
As shown in FIG. 11A, the joining margin 84 between the substrate 81 and the sealing material 1 is a region having a width of 2.0 mm that is 2.0 mm away from the end of the substrate 81 or the sealing material 1.

[Joint method I]
The room-temperature bonding apparatus shown in FIG. 6 is configured so that the substrate on which the magnesium layer is formed and the sealing material cut into a size of 50 mm × 50 mm are opposed to the magnesium layer on the substrate and the gas barrier layer of the sealing material. 100 holders 105 and 106 were set. Furthermore, a metal mask was disposed on each of the opposing surfaces of the substrate and the sealing material. The metal mask is provided with a slit in a region corresponding to the joining margin.

After the mask was placed, the substrate and the sealing material joining region were cleaned and surface activated by reverse sputtering with the ion gun 102 under a vacuum pressure of 1 × 10 ⁻⁶ Pa in the room temperature bonding apparatus 100. In reverse sputtering, Ar ions were irradiated for 1 to 10 minutes with an acceleration voltage in the range of 0.1 to 2 kV and a current value in the range of 1 to 20 mA.

Next, sputtering was performed using Si as a target, and a 20 nm silicon (Si) film was formed in a region to be joined. The sputtering was performed at an acceleration voltage of 1.5 kV and a current value of 100 mA for 3 minutes. Furthermore, surface activation treatment was performed by reverse sputtering on the silicon film. The reverse sputtering treatment conditions are the same as the reverse sputtering for the substrate and the sealing material.
After removing the metal mask and adjusting the degree of vacuum to 1 × 10 ⁻⁷ Pa, bonding was performed by bringing the bonding margin between the substrate and the sealing material into contact with each other and applying pressure of 20 MPa for 3 minutes.

  It was 50.0 nm when the tomographic photograph of the junction part of a board | substrate and a sealing material was image | photographed, and the total thickness of the silicon film between a board | substrate and a sealing material was measured as a thickness of a junction part.

[Simulated devices 102-133]
In the manufacture of the simulated device 101, as shown in Table 1 and Table 2 below, the sealing material 1 is replaced with each sealing material 2-15, the bonding method I is replaced with each bonding method II-VI, The simulated devices 102 to 133 were manufactured in the same manner as the simulated device 101 except that the thickness was changed.
Specific processing procedures of the joining methods II to VI are as follows.

[Joint Method II]
Plasma dry cleaner Model PC-300 (manufactured by Samco Co., Ltd.) using a metal mask similar to joining method I and joining each of the substrate on which the magnesium layer is formed and the sealing material cut into a size of 50 mm × 50 mm. Surface activation treatment. The surface activation treatment was performed under the treatment conditions of a degree of vacuum of 30 Pa, an oxygen flow rate of 10 ml / min, a discharge power of 100 W, and a treatment time of 5 minutes. The metal mask was removed, and the substrate and the sealing material were each exposed to an environment of a temperature of 25 ° C. and a relative humidity of 80% for 3 minutes. The joining margin was brought into contact using a vacuum laminator, and the substrate and the sealing material were joined by applying a pressure of 0.5 MPa and heating at 80 ° C. for 5 minutes to the joining margin region.
It was 0.1 nm when the tomographic photograph of the junction part of a board | substrate and a sealing material was image | photographed and the distance between a board | substrate and a sealing material was measured as the thickness of a junction part.

[Joint method III]
Plasma dry cleaner Model PC-300 (manufactured by Samco Co., Ltd.) using a metal mask similar to joining method I and joining each of the substrate on which the magnesium layer is formed and the sealing material cut into a size of 50 mm × 50 mm. Surface activation treatment. The surface activation treatment was performed under the treatment conditions of a degree of vacuum of 30 Pa, an oxygen flow rate of 10 ml / min, a discharge power of 100 W, and a treatment time of 5 minutes.

  Next, the sealing material is exposed to saturated steam at a temperature of 23 ° C. of a silane coupling agent KBM903 (3-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) for 3 minutes to form an adhesive comprising the silane coupling agent KBM903. A layer was formed. Further, the substrate is exposed to a saturated vapor of silane coupling agent KBM403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone Kogyo Co., Ltd.) at a temperature of 23 ° C. for 3 minutes to form an adhesive layer comprising the silane coupling agent KBM403. Formed.

After removing the metal mask from the sealing material and the substrate, the respective joining margins are brought into contact with each other using a vacuum laminator, and pressurization at 0.5 MPa and heating at 80 ° C. are performed for 5 minutes on the joining margin region. As a result, the substrate and the sealing material were joined.
It was 1.0 nm when the tomographic photograph of the junction part of a board | substrate and a sealing material was image | photographed, and the thickness of the contact bonding layer between a board | substrate and a sealing material was measured as the thickness of a junction part.

[Joint Method IV]
Plasma dry cleaner Model PC-300 (manufactured by Samco Co., Ltd.) using a metal mask similar to joining method I and joining each of the substrate on which the magnesium layer is formed and the sealing material cut into a size of 50 mm × 50 mm. Surface activation treatment. The surface activation treatment was performed under the treatment conditions of a degree of vacuum of 30 Pa, an oxygen flow rate of 10 ml / min, a discharge power of 100 W, and a treatment time of 5 minutes.

  Next, as a molecular adhesive, 6- (3-triethoxysilyl) propylamino) -1,3,5-triazine-2,4-dithiol monosodium (hereinafter, referred to as 5% by mass ethanol solution) A 0.2% by mass solution of TES) was prepared. After covering the area | region other than the joining margin of a sealing material with a mask material, it was immersed in the prepared solution and the heating of the temperature of 100 degreeC was performed for 15 minutes in oven. Furthermore, the sealing material was washed with ethanol and dried with a dryer to obtain a sealing material in which an adhesive layer made of TES was formed at the joining margin.

After removing the metal mask from the encapsulant, the substrate and the encapsulant are brought into contact with each other so as to match the bonding margin using a vacuum laminator, and pressurization of 0.5 MPa and heating at 80 ° C. are performed for 5 minutes. The substrate and the sealing material were joined.
It was 10.0 nm when the tomographic photograph of the junction part of a board | substrate and a sealing material was image | photographed, and the thickness of the contact bonding layer between a board | substrate and a sealing material was measured as the thickness of a junction part.

[Joint method V]
The following adhesive components were mixed and heated to 80 ° C., and then stirred and mixed uniformly at a stirring speed of 3000 rpm using a stirring mixer homodisper L type (manufactured by Primix). An adhesive was obtained.
(Adhesive material)
Epoxy resin YL983U (bisphenol F type epoxy resin that is liquid at normal temperature, manufactured by Mitsubishi Chemical Corporation): 50 parts by mass Celoxide 2021P (alicyclic epoxy resin that is liquid at normal temperature (3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxy) (Cyclohexanecarboxylate), manufactured by Daicel): 20 parts by mass Epoxy resin jER1001 (bisphenol A type epoxy resin solid at normal temperature, manufactured by Mitsubishi Chemical Corporation): 30 parts by mass Gelling agent Zefiac F351 (acrylic core-shell particles, Gantz Kasei) Manufactured): 20 parts by mass Nanoace (registered trademark) D-600 (talc having a volume average particle diameter of 0.6 μm, manufactured by Nippon Talc Co., Ltd.): 10 parts by mass Photocationic polymerization initiator CPI (registered trademark) -210S (San Apro) Manufactured): 2 parts by mass Silane coupling agent KBM-403 (γ-Gu Sid trimethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd.): 1 part by weight

The obtained adhesive was discharged by a dispenser at a discharge amount of 2 mg / cm, and the adhesive was applied to the region of the sealing material where it was to be bonded. The sealing material which apply | coated the adhesive agent was made to contact a board | substrate using the vacuum laminator, and pressurization of 0.1 MPa was performed. Thereafter, ultraviolet light with an integrated light amount of ² J / cm ² was irradiated at a temperature of 80 ° C. using a high-pressure mercury lamp, and a curing treatment for 30 minutes was performed to join the substrate and the sealing material.
It was 1000.0 nm when the tomographic photograph of the junction part of a board | substrate and a sealing material was image | photographed and the thickness of the contact bonding layer between a board | substrate and a sealing material was measured as a thickness of a junction part.

[Joint method VI]
In the joining method V, joining was performed in the same manner as the joining method V except that Nanoace (registered trademark) D-600 was removed from the components of the adhesive.
It was 100.0 nm when the tomographic photograph of the junction part of a board | substrate and a sealing material was image | photographed, and the thickness of the contact bonding layer between a board | substrate and a sealing material was measured as a thickness of a junction part.

[Evaluation]
The sealing performance when the simulated devices 101 to 133 were placed in a high-temperature and high-humidity environment and the sealing performance after the resistance test were evaluated.
The sealing performance when the simulated devices 101 to 133 were placed under high temperature and high humidity was evaluated as follows.
The simulated device was allowed to stand for 500 hours in an environment at a temperature of 85 ° C. and a relative humidity of 85%, and then the sealing material was peeled off to observe the corrosion of the magnesium layer. The ratio of the area of the corroded portion relative to the entire magnesium layer was determined, and the proportion (%) of the area of the corroded portion was evaluated as the sealing performance according to the following criteria.
◎: Corrosion is not observed and the sealing performance is very high ○: Corrosion is present, but the area ratio of the corroded portion is less than 0.5%, and the sealing performance is high △: Corrosion is present, but corrosion The proportion of the area of the portion is 0.5% or more and less than 1.5%, which is a practical sealing performance. X: Corrosion portions having an area ratio of 1.5% or more are observed, and the sealing performance is low.

In addition, as a resistance test, each simulated device was subjected to the following steps (1) to (3) for 100 cycles, and the sealing performance after the resistance test was evaluated. The evaluation method of the sealing performance is the same as the evaluation method of the sealing performance when placed in the high temperature and high humidity environment.
(1) Each simulated device was placed in an environment of temperature 25 ° C. and humidity 20% RH, and then heated to 85 ° C. over 1 hour. Furthermore, the humidity was raised to 85% over 1 hour, and the temperature was kept at 85 ° C. and humidity of 85% for 1 hour.
(2) The humidity was lowered to 20% over 1 hour, the temperature was further lowered to -35 ° C over 2 hours, and kept in an environment of temperature -35 ° C and humidity 20% for 1 hour.
(3) The temperature was raised to 25 ° C over 1 hour, and the environment was returned to a temperature of 25 ° C and a humidity of 20%.

Tables 1 and 2 below show the evaluation results.

In Table 1 and Table 2, the abbreviations described in the column of the resin of the support of the sealing body represent the following resins.
PET: Polyethylene terephthalate COP: Cycloolefin polymer PI: Polyimide PC: Polycarbonate LDPE: Low density polyethylene CPP: Unstretched polypropylene

  As shown in Table 1 and Table 2, by using a sealing material in which the Young's modulus of the support is in the range of 0.1 to 0.35 GPa, the thickness of the joint is 0.1 to 100.0 nm. It can be seen that excellent sealing performance can be exhibited even within the range and thin.

<Example II>
[Organic EL element 201]
A polyimide U-Varnish-S (manufactured by Ube Industries) was cast on a 0.7 mm thick glass substrate and baked at 350 ° C. for 30 minutes to form a 25 μm thick polyimide film. Further, on the polyimide film, a pixel portion and a driver circuit portion each having 640 pixels × 480 pixels were provided as shown in FIGS. 10A and 10B. After a Mo / Al / Mo laminate was formed so as to be in contact with the pixel portion and the drive circuit portion, it was formed into an electrode shape by a photolithography method to form a lead electrode. Thereafter, a 200 nm SiO ₂ film is formed as a protective layer by PECVD so as to cover the entire surface of the substrate, and the sealing material 1 manufactured in Example I and the substrate are bonded by the bonding method I, and FIG. An organic EL element 201 having the same configuration as the organic EL element 10B for display shown in A) and FIG.

[Organic EL elements 202 to 207]
In the production of the organic EL element 201, each organic material was changed in the same manner as the organic EL element 202 except that the sealing material 1 was replaced with the sealing material 2 and the thickness of the extraction electrode was changed as shown in Table 3 below. EL elements 202 to 207 were manufactured.

[Organic EL element 208]
In the production of the organic EL element 201, an organic EL element 208 was produced in the same manner as the organic EL element 201 except that the sealing material 1 was replaced with the sealing material 4.

[Organic EL elements 209 to 212]
In manufacturing the organic EL element 204, the organic EL elements 209 to 212 were manufactured in the same manner as the organic EL element 204 except that the sealing material 1 was replaced with the sealing material shown in Table 3 below.

<Evaluation>
A resistance test and a bending test were performed on each of the organic EL elements 201 to 212, and the sealing performance after the test was evaluated.
(Sealing performance after resistance test)
Each organic EL element 201-212 was subjected to a resistance test in which it was stored for 250 hours while flowing a current of 10 mA / cm ^{2 in} an environment of a temperature of 40 ° C. and a relative humidity of 50% RH. After the durability test, a luminescence image obtained by applying a current of 1 mA / cm ² to each of the organic EL elements 201 to 207 at room temperature was photographed, and the ratio of the area of the dark spot to the entire area of the obtained image (% ) Was calculated. The ratio of the dark spot area was evaluated as the sealing performance according to the following criteria.
A: Dark spot area ratio is 0% and sealing performance is very high B: Dark spot area ratio is greater than 0% and not more than 0.2%, and sealing performance is high Δ: Dark The area ratio of the spot is larger than 0.2% and 0.5% or less, and there is a sealing performance that can be practically used. ×: The area ratio of the dark spot is larger than 0.5%, and the sealing performance is low.

(Bending test)
Each organic EL element 201-212 was wound around a cylinder with a diameter of 10 mmφ for 1 second, and then the bending test was repeated for 100,000 cycles of unwinding over 1 second and returning it to a flat surface.
Furthermore, after storing for 250 hours in an environment of a temperature of 85 ° C. and a relative humidity of 85% RH, the sealing performance after the bending test was evaluated in the same manner as the evaluation of the sealing performance after the resistance test.

Table 3 below shows the evaluation results.
In Table 3, as in Tables 1 and 2, the resin of the sealing material support is abbreviated.

  As shown in Table 3, the thinner the extraction electrode, the easier it is to fill the gap between the extraction electrodes with a sealing material, and a good sealing performance is obtained. Moreover, it turns out that sealing performance can be improved by using the sealing material with a small Young's modulus of a support body.

<Example III>
[Encapsulant 21]
Using a Zeonor film (registered trademark) ZF-14 (a cycloolefin polymer (COP) film manufactured by Nippon Zeon Co., Ltd.) having a Young's modulus of 2.2 GPa and a thickness of 50 μm as a support, a type 04 gas barrier layer was formed as follows. The sealing material 21 was manufactured.

[Type 04 gas barrier layer]
A SiO ₂ film having a thickness of 100 nm was formed as a gas barrier layer on the support of the sealing material by PECVD under the following film formation conditions.
(Deposition conditions)
Source gas: Hexamethyldisiloxane gas, silane gas and oxygen gas are supplied so that the total flow rate of each gas is 50 sccm. Inert gas: Helium gas is supplied at a flow rate of 50 sccm Chamber pressure: 10 Pa
Substrate temperature: 60 ° C
RF power supply: 500W
RF power supply frequency: 13.56 MHz

[Sealing materials 22 to 27]
In the production of the encapsulant 21, each encapsulant is similar to the encapsulant 21 except that trimethylaluminum is added to the gas barrier layer source gas to form a SiO _x Al _z film as the gas barrier layer. 22-27 were produced.
At the time of manufacturing each sealing material 22-27, the supply ratio of hexamethyldisiloxane gas, oxygen gas and trimethylaluminum gas is adjusted, and as shown in Table 4 below, the atomic composition of oxygen atoms and aluminum atoms with respect to silicon atoms SiO _x Al _z films having different ratios x and z were formed.

[Sealant 28-33]
In the production of the sealing material 21, the raw material gas for the gas barrier layer is replaced with hexamethylsiloxane, silane, and oxygen gas, and the SiO _{x Cw} film is formed as the gas barrier layer, except that the same material as the sealing material 21 is formed. Thus, each sealing material 28-33 was manufactured.
During the production of each sealing material 28 to 33, the supply ratio of hexamethylsiloxane gas, oxygen gas and silane gas is adjusted, and as shown in Table 4 below, the atomic composition ratio x of oxygen atoms and carbon atoms with respect to silicon atoms and SiO _x C _w films with different w were formed.

[Sealing materials 34 to 38]
In the production of the sealing material 21, each of the sealing materials 21 was the same as the sealing material 21 except that oxygen gas was excluded from the source gas of the gas barrier layer and ammonia gas was added to form a SiN _y film as the gas barrier layer. Sealing materials 34 to 38 were produced.
SiN _y films having different atomic composition ratios y of nitrogen atoms to silicon atoms as shown in the following Table 4 by adjusting the supply ratio of hexamethyldisiloxane gas and ammonia gas at the time of manufacturing each sealing material 34 to 38 Formed respectively.

[Sealing materials 39 to 42]
In the production of the sealing material 21, each sealing material 39 is the same as the sealing material 21 except that ammonia gas is added to the raw material gas of the gas barrier layer to form a SiO _x N _y film as the gas barrier layer. -42 were produced.
During the production of each sealing material 39 to 42, the supply ratio of hexamethyldisiloxane gas, oxygen gas and ammonia gas is adjusted, and as shown in Table 4 below, the atomic composition ratio of oxygen atoms and nitrogen atoms to silicon atoms SiO _x N _y films with different x and y were formed.

[Encapsulant 43]
In the production of the sealing material 21, the second gas barrier layer was formed on the previously formed gas barrier layer as follows, and the sealing material 43 was produced.
Dibutyl ether solution NAX120-20 containing 1% by mass of N, N, N ′, N′-tetramethyl-1,6-diaminohexane and 19% by mass of perhydropolysilazane as an amine catalyst (manufactured by AZ Electronic Materials Co., Ltd.) ) Was added to 0.5 g of aluminum ethyl acetoacetate diisopropylate, stirred at 80 ° C. for 1 hour, and allowed to cool to prepare a coating solution for the second gas barrier layer.
In the atmosphere at 23 ° C. and 50% RH, the prepared coating liquid for the second gas barrier layer is dried to 150 nm on the first gas barrier layer previously formed. It applied by the extrusion method. After drying at room temperature for 10 minutes, under a nitrogen atmosphere in which the oxygen concentration was adjusted within the range of 0.1 to 0.01% by volume, vacuum ultraviolet rays with a wavelength of 172 nm and an integrated light amount of ² J / cm ² were irradiated at 80 ° C. A second gas barrier layer was formed.

[Sealing materials 44 to 46]
A second gas barrier layer was formed on each gas barrier layer of the sealing materials 25, 31, and 36 in the same manner as the sealing material 43, thereby manufacturing the sealing materials 44 to 46.

The atomic composition ratios x, y, z, and w of the first gas barrier layer of each sealing material 21 to 46 were confirmed by a depth profile obtained by XPS analysis of the gas barrier layer under the following analysis conditions.
(Analysis conditions)
Analyzer: QUANTERASXM (manufactured by ULVAC-PHI)
X-ray source: Monochromatic Al-α
Measurement area: Si2p, C1s, N1s, O1s, M *
(M * represents the optimum measurement region depending on the metal. For example, B1s for boron, Al2p for aluminum, Ga3d or Ga2p for gallium, In3d for indium, (In the case of thallium, it is Tl4f.)
Sputter ion: Ar (2 keV)
Depth profile: Sputtering for 1 minute and repeating the measurement, the composition was determined from the average value in the thickness direction of the gas barrier layer. Quantification: The background was determined by the Shirley method, and the relative sensitivity coefficient method was determined from the obtained peak area. Data processing quantified using: MultiPak (manufactured by ULVAC-PHI)

  When the gas barrier properties of each of the sealing materials 21 to 46 and the elongation of the gas barrier layer were measured in the same manner as in Example I, the measurement results shown in Table 4 below were obtained.

[Organic EL element 301]
A 150-nm-thick indium tin oxide (ITO) film is formed on a 40 μm-thick alkali-free glass substrate lined with a polyethylene terephthalate (PET) film, and heated at 120 ° C. for 10 minutes to be transparent. A conductive film was formed. An anode having a predetermined pattern was formed on the transparent conductive film by photolithography.

The surface of the formed anode was subjected to a charge removal process using a static eliminator with weak X-rays. Furthermore, a surface modification treatment was performed using a low pressure mercury lamp with a wavelength of 184.9 nm, an irradiation intensity of 15 mW / cm ² , and a distance between the anode and the low pressure mercury lamp of 10 mm. Thereafter, the hole transport layer coating solution was applied onto the anode by an extrusion coater so that the thickness after drying was 50 nm. The coating was performed in the atmosphere at a temperature of 25 ° C. and a relative humidity of 50% RH. The coating solution was obtained by diluting Clevios (registered trademark) P AI 4083 (polyethylenedioxythiophene / polystyrene sulfonate (abbreviation: PEDOT / PSS), Heraeus) with 65% pure water and 5% methanol. Prepared.

  The solvent was removed from the coating film at a height of 100 mm by applying hot air with a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 100 ° C. Further, using a heat treatment apparatus, a back surface heat transfer system heat treatment was performed at a temperature of 150 ° C. and dried to form a hole transport layer.

Next, the white light emitting layer coating solution was applied onto the hole transport layer by an extrusion coater so that the thickness after drying was 40 nm. The coating was performed in an atmosphere having a nitrogen gas concentration of 99% or more under coating conditions of a coating temperature of 25 ° C. and a coating speed of 1 m / min. The coating solution was prepared by dissolving the following components in 100 g of toluene.
(White light emitting layer coating solution)
Host compound HA: 1.0 g
Luminescent dopant DA: 100 mg
Luminescent dopant DB: 0.2 mg
Luminescent dopant DC: 0.2 mg

The following formula represents the structure of each of the host compound HA, the light emitting dopants DA, DB, and DC.

  The solvent was removed from the coating film at a height of 100 mm by applying hot air at a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 60 ° C. Further, a heat treatment at a temperature of 130 ° C. was performed and dried to form a light emitting layer.

On the light emitting layer, the coating liquid for the electron transport layer was applied by an extrusion coater so that the thickness after drying was 30 nm. The coating was performed in an atmosphere having a nitrogen gas concentration of 99% or more under coating conditions of a coating temperature of 25 ° C. and a coating speed of 1 m / min. Moreover, the 0.5 mass% solution obtained by melt | dissolving the following compound EA in 2,2,3,3-tetrafluoro-1-propanol was used as a coating liquid of an electron carrying layer.

The solvent was removed from the coating film at a height of 100 mm by applying warm air at a discharge air velocity of 1 m / s, a wide air velocity distribution of 5%, and a temperature of 60 ° C. Furthermore, a heat treatment at a temperature of 200 ° C. was performed and dried to form an electron transport layer.
Thereafter, the substrate was put into a vacuum chamber and the pressure was reduced to 5 × 10 ⁻⁴ Pa. Cesium fluoride prepared in advance in a tantalum vapor deposition boat in a vacuum chamber was heated to form an electron injection layer having a thickness of 3 nm on the electron transport layer.

On the electron injection layer, an aluminum film having a predetermined pattern was formed by vapor deposition using a mask under a vacuum of 5 × 10 ⁻⁴ Pa to obtain a cathode having a thickness of 100 nm.
After forming the cathode, 50 nm molybdenum / 200 nm aluminum / 50 nm molybdenum were sequentially laminated so as to overlap the anode and a part of the cathode to form an extraction electrode. As shown in FIG. 12, this lead electrode had a trapezoidal cross-sectional shape with a bottom side length of 150 μm, an upper side length of 100 μm, and a thickness of 250 nm.

Next, a SiO ₂ film having a thickness of 200 nm was formed as a protective layer by a CVD method except for the ends of the anode and the cathode.
After forming the protective layer, the protective layer and the produced sealing material 1 were joined by the joining method I described above to produce an organic EL element 301 for illumination.

[Manufacture of organic EL elements 302 to 326]
In the manufacture of the organic EL element 301, the organic EL elements 302 to 326 for illumination are manufactured in the same manner as the organic EL element 301 except that the sealing materials 22 to 46 are used instead of the sealing material 21. did.

<Evaluation>
(Sealing performance after resistance test)
Each organic EL element 301 to 326 was subjected to a resistance test in which it was stored for 250 hours in an environment of a temperature of 85 ° C. and a relative humidity of 85% RH. After the durability test, a luminescence image obtained by applying a current of 1 mA / cm ² to each of the organic EL elements 301 to 326 at room temperature was photographed, and the ratio of the area of the dark spot to the entire area of the obtained image (% ) Was calculated. The ratio of the dark spot area was evaluated as the sealing performance according to the following criteria.
A: Dark spot area ratio is 0% and sealing performance is very high B: Dark spot area ratio is greater than 0% and not more than 0.2%, and sealing performance is high Δ: Dark The area ratio of the spot is larger than 0.2% and 0.5% or less, and there is a sealing performance that can be practically used. ×: The area ratio of the dark spot is larger than 0.5%, and the sealing performance is low.

(Sealing performance after bending test)
Each organic EL element 301 to 326 was wound around a cylinder with a diameter of 10 mmφ for 1 second, and then the bending test was repeated for 100,000 cycles of unwinding for 1 second and returning to a flat surface.
Furthermore, after storing for 100 hours in an environment of a temperature of 85 ° C. and a relative humidity of 85% RH, the sealing performance after the bending test is determined from the ratio of the dark spot area in the same manner as the evaluation of the sealing performance after the resistance test. evaluated.

Table 4 below shows the evaluation results.
In Table 4, as in Tables 1 and 2, the resin of the support for the sealing material is abbreviated.

  As shown in Table 4, the greater the elongation of the gas barrier layer, the better the sealing performance of the sealing material. Therefore, if the gas barrier layer has a large elongation, the Young's modulus is low and the flexibility is high. It can be seen that it is easy to follow the deformation of the high support and it is easy to fill the gap generated by the extraction electrode.

<Example IV>
[Sealing materials 51 to 55]
In the production of the sealing materials 2, 8, 6, 4 and 1 of Example I, the gas barrier layer of type 03 described above was formed instead of the gas barrier layer of type 01, and each of the sealing materials 51 to 55 was produced. did.

[Organic EL element 401]
In the manufacture of the organic EL element 301 of Example III, the organic EL element 301 was used in the same manner as the organic EL element 301 except that the sealing material 51 was used instead of the sealing material 21 and the thickness of the extraction electrode was changed to 400 nm. Element 401 was manufactured.

[Organic EL elements 402 to 406]
In the manufacture of the organic EL element 401, as shown in Table 5 below, the organic EL elements 402 to 406 are formed in the same manner as the organic EL element 401 except that the bonding method I is changed to the bonding methods II to VI. Manufactured.

[Organic EL elements 407 to 410]
In the manufacture of the organic EL element 402, as shown in Table 5 below, each organic EL element 407 to 407 is similar to the organic EL element 402 except that the sealing material 51 is replaced with each sealing material 52 to 55. 410 was produced.

<Evaluation>
The gas barrier properties of the sealing material 51 and the elongation of the gas barrier layer were measured in the same manner as in Example I.
Further, in the same manner as in Example III, the organic EL elements 401 to 410 were subjected to a resistance test and a bending test, and the sealing performance after each test was evaluated.

Table 5 below shows the evaluation results.
In Table 5, as in Tables 1 and 2, the resin of the sealing material support is abbreviated.

  As shown in Table 5, it can be seen that when the joint is thin and the thickness is in the range of 0.1 to 100.0 nm, the sealing performance is high. Moreover, it turns out that sealing performance is improving, so that a Young's modulus is small and a sealing material with high flexibility is high.

DESCRIPTION OF SYMBOLS 10 Organic EL element 1 for illumination board | substrate 2 main body unit 3 sealing material 31 support body 32 gas barrier layer 4 extraction electrode 5 junction part 6 protective layer 10B organic EL element 200 for display main body unit 201 pixel part 202 drive circuit part 100 Room temperature bonding device 102 Ion gun 103-106 Holder T1, T2 Target

Claims (6)

An electronic device in which a main unit on a substrate is sealed with a sealing material,
The substrate and the sealing material are joined with a lead electrode formed so as to be exposed from the main unit,
The thickness of the joint between the substrate and the sealing material is in the range of 0.1 to 100.0 nm,
The sealing material comprises a gas barrier layer and a support for the gas barrier layer,
An electronic device having a Young's modulus at a temperature of 25 ° C of the support in a range of 0.1 to 3.5 GPa.   The electronic device according to claim 1, wherein a thickness of the extraction electrode is in a range of 10 to 500 nm.   The electronic device according to claim 1, wherein an elongation percentage of the gas barrier layer is in a range of 0.5 to 5.0%.   The said joining part contains the activation layer obtained by carrying out the surface activation process of each joining surface of the board | substrate with which the said extraction electrode was formed, and the said sealing material. The electronic device as described in any one of the above.   The joint includes an activation layer obtained by subjecting each of a metal layer formed on the substrate on which the extraction electrode is formed and a metal layer formed on the sealing material to surface activation treatment. The electronic device according to any one of claims 1 to 3, characterized in that:   The electronic device according to any one of claims 1 to 3, wherein the bonding portion includes an adhesive layer in which a silane coupling agent or a molecular adhesive is used.

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