CN107251649A - Organnic electroluminescent device - Google Patents
Organnic electroluminescent device Download PDFInfo
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- CN107251649A CN107251649A CN201680009199.1A CN201680009199A CN107251649A CN 107251649 A CN107251649 A CN 107251649A CN 201680009199 A CN201680009199 A CN 201680009199A CN 107251649 A CN107251649 A CN 107251649A
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical class C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- NESLVXDUKMNMOG-UHFFFAOYSA-N triethoxy-(propyltetrasulfanyl)silane Chemical compound CCCSSSS[Si](OCC)(OCC)OCC NESLVXDUKMNMOG-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical class CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZBZHVBPVQIHFJN-UHFFFAOYSA-N trimethylalumane Chemical compound C[Al](C)C.C[Al](C)C ZBZHVBPVQIHFJN-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
- H10K59/8731—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- Electroluminescent Light Sources (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
The present invention provides a kind of organic el device, and it has：Device substrate；Organic EL element, is formed at device substrate；And gas barrier film, cover organic EL element and engaged with device substrate, in gas barrier film, the surface of combination with more than 1 group of substrate organic layer and inorganic layer is inorganic layer, and inorganic layer is engaged towards device substrate, the 1st conversion zone of device substrate side is engaged through with the reaction between the 2nd conversion zone of gas barrier film side that is bonded of the 1st conversion zone to carry out, the distance in junction surface between device substrate and organic layer away from its nearest neighbours is below 100nm.Thus there is provided the height of the gas barrier property for sealed junction surface and the organic el device of service life length.
Description
Technical field
The present invention relates to a kind of Organnic electroluminescent device that organic electroluminescent device is sealed by gas barrier film.
Background technology
Organic electroluminescent device (organic EL element) is weak to the resistivity of moisture.Therefore, in order to assign gas barrier property, make
There is the knot by attachment sealing organic el element with the Organnic electroluminescent device (organic el device) of organic EL element
Structure.
Generally, the sealing of the organic EL element for assigning gas barrier property is carried out using glass.However, glass is heavier and resistance to punching
Hitting property is also weaker.
In contrast, for the purpose of lightweight, raising of impact resistance etc., have studied thin by the plastics with gas barrier layer
Film is the content of gas barrier film sealing organic el element.Also, organic EL element is formed on flexible substrate and by resistance
Gas film sealing organic EL element, is thus obtained with flexible organic el device.
For example, having recorded following organic el device in patent document 1：It is to pass through the 1st substrate, the 2nd substrate and junction surface
The organic el device of sealing organic el element, using gas barrier film as the 1st substrate and the 2nd substrate, junction surface passes through the 1st substrate
Reaction between reactive functional groups on surface and the reactive functional groups on the surface of the 2nd substrate is bonded together to form.
Also, following organic EL element has been recorded in patent document 2：With organic EL element, clamping organic EL element and
A pair of the gas barrier films and barrier part connected in end, the region adjoined one another in a pair of gas barrier films is provided with recess, barrier
The end face of part covering gas barrier film and the part provided with recess.
Also, barrier part is bonded using adhesives such as epoxy resin and by crimping etc. with gas barrier film.
In addition, having recorded following organic el device in patent document 3：Organic EL element is clamped using 2 gas barrier films and is led to
The periphery of heat fusing or adhesive bonding gas barrier film is crossed, organic EL element is thus sealed.
Also, as adhesive, preferably use with epoxy radicals, amino, the polyurethane series of hydroxyl adhesive.
Conventional art document
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-218805 publications
Patent document 2：Japanese Unexamined Patent Publication 2010-205503 publications
Patent document 3：Japanese Unexamined Patent Publication 2003-327718 publications
The content of the invention
The invention technical task to be solved
When manufacturing organic el device etc., as shown in patent document 3, carried out usually using adhesive this based on choke
The sealing of film.Here, the deterioration in order to prevent organic EL element, is not only gas barrier film, also required that for sealed junction surface
High-gas resistance.
That is, even if sealing organic EL element by gas barrier film, but if from as the bonding for sealed junction surface
Oxidant layer invades moisture, then organic EL element can be caused to be deteriorated because of moisture.Especially, when the gas barrier properties of gas barrier film are higher, lead to
The moisture of junction surface intrusion is crossed far more than the moisture invaded by gas barrier film, due to the moisture invaded from junction surface cause it is organic
EL element is deteriorated.
On the sealing of the organic EL element based on gas barrier film, there is also the method using the high adhesive of gas barrier property.So
And, the high adhesive of gas barrier property solidifies because of light and heat mostly, can make the flexible deterioration of organic el device.
In contrast, as Patent Document 1, with anti-between the compound based on the surface for being present in gas barrier film
The molecular bond answered is carried out for the engagement by gas barrier film sealing organic el element, so as to make junction surface very thin, because
This can suppress the intrusion of the moisture from junction surface.
However, according to the research of the present inventor, the bonding force of conventional molecular bond is insufficient, cause to produce at junction surface
Gas barrier film floats and peeled off, it is impossible to the appropriate sealing for carrying out the organic EL element based on gas barrier film.
It is an object of the invention to solve this problem of the prior art point, it is that provide one kind seals by gas barrier film
In the organic el device of organic EL element, the sealing of organic EL element can be reliably carried out, and prevented from engagement
The organic el device of the service life length of the intrusion of the moisture in portion.
Means for solving technical task
In order to solve the problem points, there is provided a kind of Organnic electroluminescent device, it is characterised in that organic electronic of the invention
Light-emitting device has：Device substrate；Organic electroluminescent device, is formed at device substrate；And gas barrier film, covering organic electroluminescence hair
Optical element and engaged with device substrate and seal organic electroluminescent device,
In gas barrier film, there is the group of more than 1 group of inorganic layer and the organic layer of the substrate as inorganic layer on supporter
Close, surface is inorganic layer, and the inorganic layer on surface is engaged towards device substrate,
Between device substrate and the 1st conversion zone and the 2nd conversion zone that are engaged through being arranged on device substrate of gas barrier film
Reaction carry out, the 2nd conversion zone is arranged on gas barrier film and is bonded with the 1st conversion zone,
Between the junction surface of device substrate and gas barrier film, the nearest organic layer of distancing element substrate and device substrate away from
From for below 100nm.
In this Organnic electroluminescent device of the invention, the preferred face for forming organic layer and inorganic layer of supporter
Surface roughness Ra is below 30nm.
Also, the thickness of the organic layer on the surface of supporter is preferably formed in for more than 0.1 μm.
Also, it is preferred that the end of gas barrier film is by adhesive coverage.
Also, the surface roughness Ra in the face of the formation organic electroluminescent device of preferred element substrate is below 5nm.
Also, it is preferred that the width at junction surface is 0.5~5mm.
Also, it is preferred that the thickness of inorganic layer is 10~45nm.
Also, preferred element substrate is following gas barrier film, the gas barrier film has more than 1 group of inorganic layer on supporter
Combination and surface with the organic layer of the substrate as inorganic layer are inorganic layer, and form Organic Electricity on the inorganic layer on surface
Electroluminescent element.
Furthermore it is preferred that the 1st conversion zone contains silane coupler, the 2nd conversion zone contains and the silane contained by the 1st conversion zone
The silane coupler that coupling agent reacts, by the silane coupler of the 1st conversion zone and the silane coupler of the 2nd conversion zone it
Between reaction carry out the engagement of device substrate and gas barrier film.
Invention effect
According to this present invention, the Organnic electroluminescent device of organic electroluminescent device is being sealed by gas barrier film
In, the sealing of organic electroluminescent device can be reliably carried out, and prevent the intrusion of the moisture from junction surface to make
With the Organnic electroluminescent device of long lifespan.
Brief description of the drawings
Fig. 1 is the figure of one for conceptually representing the Organnic electroluminescent device of the present invention.
Fig. 2 is the figure of another for conceptually representing the Organnic electroluminescent device of the present invention.
Fig. 3 is the illustration for conceptually representing the gas barrier film in the Organnic electroluminescent device for the present invention.
Embodiment
Hereinafter, preference shown with reference to the accompanying drawings, the Organnic electroluminescent device of the present invention is described in detail.
One of the Organnic electroluminescent device of the present invention is conceptually represented in Fig. 1.In addition, in following explanation, also will
" organic electroluminescent " is referred to as " organic EL ".
In the organic el device of the present invention, organic EL element is sealed by gas barrier film.
Organic el device 10 shown in Fig. 1 substantially has device substrate 12, organic EL element 14 and a gas barrier film 16 and structure
Into.Organic el device 10 superimposed elements substrate 12 and gas barrier film 16 in the way of covering organic EL element 14, in gas barrier film 16
Periphery, by the attaching components substrate 12 of junction surface 18 and gas barrier film 16, so as to pass through the sealing organic el element 14 of gas barrier film 16.
Also, though diagram is eliminated, for the device substrate 12 of sealing organic el element 14 and connecing for gas barrier film 16
In conjunction portion 18, the 1st conversion zone is provided with device substrate 12, provided with the 2nd reaction being bonded with the 1st conversion zone on gas barrier film 16
Layer.Junction surface 18 is formed by the reaction between the 1st conversion zone and the 2nd conversion zone.
Device substrate 12 can utilize the various shapes in the various organic EL elements such as organic el display or organic EL illuminating
It is used as the known tablet or tympan of substrate in.
For device substrate 12, as one, illustration has by polyethylene terephthalate (PET), poly- naphthalene diformazan
Sour glycol ester (PEN), polyethylene (PE), polypropylene (PP), polystyrene, polyamide, polyvinyl chloride, makrolon, poly- third
Alkene nitrile, polyimides, polyacrylate, polymethacrylates, makrolon (PC), cyclic olefin polymer (COP), cycloolefin
It is thin that the various resin materials (high polymer material) such as copolymer (COC), triacetyl cellulose (TAC), clear polyimides are constituted
Membranoid substance or tablet, glass plate, thin glass, metallic plate etc..
, can also be preferably by gas barrier film 16 described later as device substrate 12.By the way that gas barrier film 16 is used as into element base
Plate 12, prevents the intrusion of the moisture from the side of device substrate 12 and obtains the longer organic el device 10 of service life.
When gas barrier film 16 is used as into device substrate 12, the face for forming organic EL element 14 both can be inorganic layer 28,
Can be supporter 24 (reference picture 3), but from the viewpoint of it can suitably prevent that moisture from invading the grade of organic EL element 14, it is excellent
It is selected in formation organic EL element 14 on inorganic layer 28.
The thickness of device substrate 12 is suitably set according to species or size of organic el device 10 etc..
Here, from the viewpoint of it can realize the grade of organic el device 10 with flexibility, the thickness of preferred element substrate 12
Degree is set to can obtain required flexible thickness according to material etc. is formed.
Also, composition surface of the face of the formation organic EL element 14 on device substrate 12 i.e. with gas barrier film 16 is more flat, after
Bonding force in the junction surface 18 stated becomes higher.
If considering this point, the surface roughness Ra (arithmetic in the face of the formation organic EL element 14 of preferred element substrate 12
Average roughness Ra) it is below 5nm, more preferably below 1nm.
, can by the way that the surface roughness Ra in the face of the formation organic EL element 14 of device substrate 12 is set into below 5nm
Make the bonding force in junction surface 18 stronger.
In addition, in the present invention, surface roughness Ra is determined according to JIS B 0601 (2001).
This organic EL element 14 for being formed at device substrate 12 is following known organic EL element (organic EL device),
It, which is constituted, has transparent electrode layer (TFT (thin film transistor (TFT))), hole injection layer, hole transmission layer, luminescent layer, hole barrier
The organic el devices such as the organic el display or organic EL illuminating of layer, electron transfer layer, electron injecting layer, negative electrode etc. (OLED).
In the organic el device 10 of the present invention, in the gas barrier film 16 of sealing organic el element 14, have 1 on supporter
The combination of the inorganic layer and the organic layer of the basalis as the inorganic layer of the group above, and surface is inorganic layer.In other words, surface
Refer to from the superiors in the stacking that supporter is proceeded by.
Gas barrier film 16 by make the inorganic layer on surface towards device substrate 12 and cover organic EL element 14 and with element base
Plate 12 is engaged, so that sealing organic el element 14.
One of gas barrier film is conceptually represented in Fig. 3.In illustrating below, also " gas barrier film " is referred to as " Obstruct membrane ".
Obstruct membrane 16 shown in Fig. 3 is sequentially laminated with organic layer 26, inorganic layer 28, organic layer 26, nothing on supporter 24
Machine layer 28.Gas barrier layer is formed by alternately laminated organic layer 26 and inorganic layer 28.
In addition, the Obstruct membrane shown in Fig. 3 has the combination of 2 groups of organic layers 26 as substrate and inorganic layer 28, but this hair
It is bright to be not limited to this.That is, the Obstruct membrane for the present invention can only have the combination of 1 group of organic layer 26 and inorganic layer 28,
There can be the combination of more than 3 groups of organic layer 26 and inorganic layer 28.
The combination of organic layer 26 and inorganic layer 28 is more, and gas barrier property can be higher.On the contrary, the group of organic layer 26 and inorganic layer 28
Close more, Obstruct membrane can be thicker, the transparency and flexibility can also decline.Therefore, organic layer 26 and the quantity of the combination of inorganic layer 28
Suitably set according to required gas barrier property, flexibility, optical characteristics etc..
But, no matter with which kind of Rotating fields in the case of, the surface of Obstruct membrane used in the present invention is inorganic layer
28。
In Obstruct membrane 16, supporter 24 is used to support organic layer 26 and inorganic layer 28.
Supporter 24 can utilize the various known materials being utilized as the supporter of Obstruct membrane.
Specifically, as supporter 24, preferably illustrate by PET, PEN, PE, PP, polystyrene, polyamide, polychlorostyrene
It is ethene, makrolon, polyacrylonitrile, polyimides, polyacrylate, polymethacrylates, PC, COP, COC, TAC, transparent
Tympan or tablet that the various resin materials such as polyimides (high polymer material) are constituted.
It is preferred that the surface roughness Ra in the face for forming organic layer 26 and inorganic layer 28 of supporter 24 is below 30nm, it is more excellent
Elect below 20nm, especially preferably below 10nm as.
In the organic el device 10 of the present invention, Obstruct membrane 16 has the organic layer 26 of the basalis as inorganic layer 28,
It can be described in detail afterwards.The surface of organic layer 26 is very high, by forming inorganic on the high organic layer 26 of surface
Layer 28, it is possible to increase the surface of the inorganic layer 28 on surface.In the organic el device 10 of the present invention, it is used as by that will have
The high inorganic layer 28 of the surface of the organic layer 26 of substrate is sealed as the composition surface of Obstruct membrane 16 and device substrate 12
Organic EL element 14, so that with based on the 1st conversion zone for being formed at device substrate 12 and the 2nd reaction for being formed at Obstruct membrane 16
High adhesion is realized in the junction surface 18 of the molecular bond bonding of reaction between layer.
Here, the surface of inorganic layer 28 is higher, the bonding force at junction surface 18 can be higher.Put down on the surface of organic layer 26
Smooth property is higher, and the surface of inorganic layer 28 can be higher.Also, in order to improve the surface of organic layer 26, preferably prop up
The surface of support body 24 is high.
That is, by by the surface roughness Ra of the formation organic layer 26 of supporter 24 and the face of inorganic layer 28 be set to 30nm with
Under, in the case that organic layer 26 is relatively thin, it also can more stably improve the surface of the inorganic layer 28 on surface, energy
Enough bonding forces for more improving junction surface 18.
The thickness of supporter 24 is suitably set according to purposes of organic el device 10 etc..Specifically, preferably prop up
The thickness of support body 24 is 20~120 μm.
By the way that the thickness of supporter 24 is set into more than 20 μm, from can suppress by formation organic layer 26 and nothing described later
The curling produced during machine layer 28, the viewpoint such as mechanical strength for being able to ensure that organic el device 10 consider it is preferred.
Also, by the way that the thickness of supporter 24 is set into less than 120 μm, from the flexible good of organic el device 10 can be made
Well, it is preferred to realize that the viewpoints such as the lightweight of organic el device 10, the filming for realizing organic el device consider.
Alternatively, it is also possible to form protective layer, adhesive layer, light reflection as needed at least one face of supporter 24
Layer, anti-reflection layer, light shield layer, planarization layer, cushion, stress relaxation layer etc., the layer (film) for obtaining various functions.
The organic layer 26 and inorganic layer 28 for constituting barrier layer are alternately laminated with one face of supporter 24.That is, it is of the invention
The middle Obstruct membrane 16 used has the stepped construction of organic and inorganic.
Organic layer 26 is the layer being made up of organic matter, is by obtained by the organic matter crosslinking (polymerization) as organic layer 26.
Organic layer 26 plays a role as the basalis for being properly formed the inorganic layer 28 for showing barrier.Pass through tool
Have this organic layer 26 as substrate, can realize the face to form inorganic layer 28 planarization and homogenization and as be suitable to shape
Into the state of inorganic layer 28.Thus, with the stacking being laminated with as the organic layer 26 of substrate and the organic and inorganic of inorganic layer 28
The Obstruct membrane 16 of structure gapless in entire surface, can form appropriate inorganic layer 28, show excellent barrier.
Also, in the present invention, there is organic layer 26 by Obstruct membrane 16, improve surface and become and device substrate 12
The flatness of the inorganic layer 28 on composition surface, so as to improve the bonding force at junction surface 18.It can be described in detail on this point after.
The formation material of organic layer 26 can utilize various known organic matters.
Specifically, polyester, acrylic resin, methacrylic resin, methacrylic acid-maleic acid are preferably illustrated common
Polymers, polystyrene, transparent fluororesin, polyimides, fluorinated polyimide, polyamide, polyamidoimide, polyetherimide
Amine, cellulose acylate, polyurethane, polyether-ether-ketone, makrolon, ester ring type polyolefin, polyarylate, polyether sulfone, polysulfones, fluorenes ring
The thermoplastic resins such as modified polycarbonate, alicyclic modified makrolon, fluorenes ring modified poly ester, acryloyl compounds or poly- silica
The film of alkane, other organo-silicon compound.These can be simultaneously using multiple.
Wherein, consider that there is radical polymerization preferably in functional group from the viewpoint such as glass transition temperature or excellent strength
The organic layer 26 that the polymer of conjunction property compound and/or the cationically polymerizable compound of ether is constituted.
Wherein, in addition to above-mentioned intensity, also from transparent high and optical characteristics is excellent etc., viewpoint considers, particularly preferred example
Show the polymer of monomer using acrylate and/or methacrylate or oligomer as principal component, glass transition temperature
Acrylic resin or methacrylic resin for more than 120 DEG C are used as organic layer 26.
Wherein, DPG two (methyl) acrylate (DPGDA), 1,9- nonanediols two (methyl) third are particularly preferably illustrated
Olefin(e) acid ester (A-NOD-N), 1,6 hexanediol diacrylate (A-HD-N), trimethylolpropane tris (methyl) acrylate
(TMPTA), (modification) bisphenol-A two (methyl) acrylate, dipentaerythritol six (methyl) acrylate (DPHA) etc., with 2 officials
The polymer of the monomer of acrylate and/or methacrylate more than energy etc. is the acrylic resin or methyl-prop of principal component
Olefin(e) acid resin.Also, further preferably use these multiple acrylic resins or methacrylic resin.
By by acrylic resin or methacrylic resin, acrylic resin or methyl-prop especially more than 2 functions
Olefin(e) acid resin formation organic layer 26, inorganic layer 28 can be formed in the firm substrate of skeleton, therefore, it is possible to formed it is finer and close and
The high inorganic layer 28 of barrier.
Thickness of the thickness of organic layer 26 according to the Obstruct membrane 16 as target, the organic layer 26 and inorganic layer as substrate
Quantity, species of inorganic layer 28 of 28 combination etc. and suitably set.
Specifically, the thickness of preferably organic layer 26 (is wherein especially formed at the organic layer 26 on the surface of supporter 24
Thickness) be more than 0.1 μm, more preferably more than 0.5 μm.It has been observed that the surface of organic layer 26 is higher, it can more carry
Bonding force in high junction surface 18.By the way that the thickness of organic layer 26 is set into more than 0.1 μm, the table of supporter 24 is suitably filled with
Face bumps and obtain the high organic layer 26 of surface.Also, by the way that the thickness of organic layer 26 is set into more than 0.1 μm,
Organic layer 26 plays a role as appropriate stress-buffer layer, therefore, it is possible to prevent inorganic in such as bending organic el device 10
The rupture of layer 28.
Also, it is preferred that the thickness of organic layer 26 is less than 3 μm, more preferably less than 1.5 μm.By by the thickness of organic layer 26
Degree is set to less than 3 μm, can suitably prevent the bad of because caused by discharging the moisture from organic layer 26 organic EL element 14
Change.
Organic layer 26 is formed using the known method of the formation material based on organic layer 26.
Generally, organic layer 26 is formed by following so-called rubbing method：Prepare containing organic solvent, as organic layer 26
The painting of polymerizable compound (monomer, dimer, tripolymer, oligomer, polymer etc.), surfactant, silane coupler etc.
Cloth composition (coating), the coating fluid is coated, dried, further irradiates etc. to make polymerization as desired by ultraviolet
Property compound polymerization (crosslinking).Also, by using rubbing method, by so-called levelling effect, surface can be formed
Very high organic layer 26.
In Obstruct membrane 16, inorganic layer 28 mainly shows barrier.
The formation material of inorganic layer 28 can utilize the various materials being made up of the inorganic matter for showing barrier.
Specifically, aluminum oxide, magnesia, tantalum oxide, zirconium oxide, titanium oxide, tin indium oxide (ITO) etc. are preferably illustrated
Metal oxide；The metal nitrides such as aluminium nitride；The metal carbides such as aluminium carbide；Silica, silicon oxynitride, silicon oxide carbide, nitrogen
The Si oxides such as Zirconia/silicon carbide；The silicon nitrides such as silicon nitride, carbonitride of silicium；The silicon carbides such as carborundum；Their hydride；
Their mixture of more than two kinds；And the inorganic compound such as their hydrogenous material.
Especially, from transparent high and from the viewpoint of can showing excellent barrier, preferably using silicon nitride, oxidation
Silicon, silicon oxynitride, aluminum oxide.Wherein, silicon nitride is in addition to excellent barrier, and the transparency is also high, therefore particularly preferably makes
Use silicon nitride.
The thickness of inorganic layer 28 according to required barrier, as target Obstruct membrane 16 thickness, be used as substrate
Quantity of combination of organic layer 26 and inorganic layer 28 etc. and suitably set.
Specifically, preferably the thickness of inorganic layer 28 is more than 10nm, more preferably more than 15nm.By by inorganic layer 28
Thickness be set to more than 10nm, good gas barrier property can be obtained.
Also, it is preferred that the thickness of inorganic layer 28 is below 45nm, more preferably below 35nm.By by the thickness of inorganic layer 28
Degree is set to below 45nm, can prevent the rupture of inorganic layer 28 in bending organic el device 10.Also, it has been observed that inorganic layer
28 surface is higher, can more strengthen the bonding force at junction surface 18, and by the way that the thickness of inorganic layer 28 is set into 45nm
Hereinafter, the surface of inorganic layer 28 can be made to follow the high surface of organic layer 26 and uprise.
Inorganic layer 28 passes through the formation of known method according to the formation material of inorganic layer 28.
Generally, inorganic layer 28 by the vapour deposition processes such as plasma CVD, sputtering, vacuum evaporation (gas phase membrane formation process) come
Formed.
In the organic el device 10 of the present invention, using with more than 1 group of the organic layer 26 and inorganic layer 28 as substrate
Combination and surface be inorganic layer 28 Obstruct membrane 16, make inorganic layer 28 towards device substrate 12 and seal be formed at device substrate
Organic EL element 14 on 12.
Also, in the organic el device 10 of the present invention, with anti-based on the 1st conversion zone and the 2nd for being arranged on device substrate 12
Answer the molecular bond of the reaction between layer carry out the device substrate 12 in the junction surface 18 for sealing organic el element 14 with
The bonding of Obstruct membrane 16, the inorganic layer on the surface that the 2nd conversion zone is bonded with the 1st conversion zone and is arranged on Obstruct membrane 16
28。
In addition, in the organic el device 10 of the present invention, the organic layer 26 nearest apart from device substrate 12 in junction surface 18
The distance between surface and device substrate 12 be below 100nm.
The present invention is by with this structure, so as to have sufficient bonding force in junction surface 18, moreover, by that will connect
The thickness in conjunction portion 18 is set to very thin, prevents the intrusion of the moisture from junction surface 18 so as to realize, inhibits because moisture causes
Organic EL element 14 deterioration and the organic el device 10 of service life length.
It has been observed that generally, Obstruct membrane is bonded on device substrate by adhesive to carry out based on the organic of Obstruct membrane
The sealing of EL element.However, in the encapsulating method, moisture can be invaded by adhesive phase, caused organic by the moisture
EL element is deteriorated.
In contrast, in the molecular bond that utilization as Patent Document 1 is bonded, due to the very thin thickness at junction surface,
Therefore moisture will not be invaded from junction surface, can prevent the deterioration of the organic EL element caused by the moisture invaded from junction surface,
The reaction between compound on the composition surface of the bonding based on the part for being present in sealing organic el element.
Here, according to the research of the present inventor, when being formed at the organic EL element of device substrate by Obstruct membrane sealing,
In order to obtain sufficient bonding force by molecular bond at junction surface, it is critically important to make the flatness height on the composition surface of Obstruct membrane
's.
That is, molecular bond is present in the compound on the surface of device substrate by silane coupler etc. and is present in Obstruct membrane
The compound on surface react and be bonded to carry out.Therefore, if the surface of Obstruct membrane is low, composition surface that
It is closely sealed insufficient between this, also, reaction between compound in composition surface do not carry out fully, even if in addition, entering
Row reaction, is also easily caused dissociation and can not obtain sufficient bonding force.
It has been observed that inorganic layer is generally formed by vapour deposition process, therefore follow the bumps of film forming face.Therefore, such as patent
In the only Obstruct membrane with inorganic layer described in document 1, the bumps of supporter are followed on the surface of inorganic layer, therefore can not be abundant
Make the surface of Obstruct membrane flat.Therefore, it is closely sealed insufficient between the Obstruct membrane and device substrate in junction surface, connect based on molecule
The bonding force of conjunction is low, causes to produce floating and peeling off for gas barrier film at junction surface, it is impossible to suitably carry out having based on gas barrier film
The sealing of machine EL element.
By thickening inorganic layer, it can be ensured that flatness to a certain degree, but nonetheless, the flat of inorganic layer can not be also said
Smooth property fully, in addition, inorganic layer can be caused to become fragile, and also has the problem of causing to lose flexibility.
In contrast, in the organic el device 10 of the present invention, Obstruct membrane 16 has the organic of the substrate as inorganic layer 28
Layer 26.That is, inorganic layer 28 is formed on organic layer 26.
It has been observed that organic layer 26 is generally formed by rubbing method.The organic layer 26 formed by rubbing method fills support
The bumps on the surface of body 24, and the effect for the levelling for passing through coating composition and with very flat (smooth) surface.And
And, also it is illustrated before, inorganic layer 28 is generally formed by vapour deposition process, therefore follows the surface shape of organic layer 26
Shape.As a result, in the present invention, the surface of inorganic layer 28 is that the high surface of organic layer 26 is followed on the surface of Obstruct membrane 16
And with very high flatness.
Therefore, in organic el device 10 of the invention, by the high surface of Obstruct membrane 16, device substrate can be made
12 the 1st conversion zone and the 2nd conversion zone of Obstruct membrane 16 is fully closely sealed, and is sufficiently carried out being formed the chemical combination of two conversion zones
The reaction and bonding of thing.As a result, in junction surface 18, can be with high adhesion joint element substrate 12 by molecular bond
With Obstruct membrane 16.Also, the junction surface 18 under the molecular bond of the reaction between the compound based on this surface is very thin,
Therefore the intrusion of the moisture from junction surface 18 can also be prevented.
In addition, compared with inorganic layer 28, organic layer 26 is rich in flexibility.Therefore, impacted or organic EL dresses from outside
When putting 10 bending, the stress that junction surface 18 is subject to obtains relaxation, additionally it is possible to pass through the straining element substrate 12 of junction surface 18 and barrier
Film 16 is peeled off.
Forming the 1st conversion zone of the device substrate 12 at junction surface 18 and the 2nd conversion zone of Obstruct membrane 16 can utilize and contain
The various layers for the compound for reacting with each other and being bonded.
That is, it is at the light irradiation by heating, ultraviolet etc. to form the 1st conversion zone and the compound of the 2nd conversion zone
Reason, electron beam irradiation processing etc. and can react and be bonded (preferably covalently bonding) with the compound of another conversion zone
Compound.
As one, can enumerate with vinyl, epoxy radicals, styryl, acryloyl group, methylacryloyl, amino,
The compound of urea groups, sulfydryl, thioether group, NCO, carboxyl, aldehyde radical etc..
As the combination for the compound for forming the 1st conversion zone and the 2nd conversion zone, as long as the chemical combination of key can be formed each other
The combination of thing, then be not particularly limited, it can be considered that the species of device substrate 12 or Obstruct membrane 16, the processing for forming key
Method or condition etc. and suitably determine.
In the present invention, according to the height of reactivity, it is used as the group for the compound for forming the 1st conversion zone and the 2nd conversion zone
Close, preferably the combination of the compound with amino and the compound with epoxy radicals.It can be the compound to form the 1st conversion zone
With amino, the compound that forming the compound of the 2nd conversion zone has the 1st conversion zone of epoxy radicals or formation has ring
Epoxide, forming the compound of the 2nd conversion zone has amino.
In order to be properly formed the 1st conversion zone in device substrate 12, preferably comprise the compound of the 1st conversion zone except with
Beyond the position being bonded with the compound of the 2nd conversion zone, the position being also bonded with the surface with device substrate 12.
Also, more preferably the compound is that have the position being bonded with the compound of the 2nd conversion zone an end, and another
Individual end has the compound at the position being bonded with the surface of device substrate 12.Also, constitute the compound of the 1st conversion zone
Can be two or more, but preferably a kind.
On the other hand, in order to be properly formed the 2nd conversion zone on the surface of Obstruct membrane 16 (inorganic layer 28), is preferably comprised
The compound of 2 conversion zones in addition to the position being bonded with the compound with the 1st conversion zone, also with Obstruct membrane 16
The position that is bonded of surface.Also, more preferably the compound is that an end there is the compound with the 1st conversion zone to enter
The position that line unit is closed, and there is the compound at the position being bonded with the surface of Obstruct membrane 16 in another end.Also, structure
Compound into the 2nd conversion zone can be two or more, but preferably a kind.
As preferred one, the 1st conversion zone is formed on device substrate 12, the 1st conversion zone is by an end
The position being bonded with the compound of the 2nd conversion zone is formed, and in another end there is the surface with device substrate 12 to enter
The compound at the position that line unit is closed is constituted.Also, in the 2nd conversion zone of formation of Obstruct membrane 16, the 2nd conversion zone is by an end
Portion has the position being bonded with the compound of the 1st conversion zone, and in another end there is the surface with Obstruct membrane 16 to enter
The compound at the position that line unit is closed is constituted.On this basis, by the compound of the 1st conversion zone that makes to form device substrate 12 with
Form the compound directly reaction of the 2nd conversion zone of Obstruct membrane 16 and be bonded, so as to form junction surface 18.
As formed the 1st conversion zone compound and formed the 2nd conversion zone compound, preferably use at one end with formation
The compound of another conversion zone reacts and has siloxanes key (Si-O) silane coupler in the other end.
As silane coupler, specifically, vinyltrimethoxy silane, VTES etc. can be illustrated
Silane coupler with vinyl；2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- glycidoxypropyls
Methyl dimethoxysilane, 3- glycidoxypropyltrimewasxysilanes, 3- glycidoxypropyl diethoxies
Base silane, 3- glycidoxypropyl triethoxysilanes etc. have the silane coupler of epoxy radicals；P- styryl front threes
TMOS etc. has the silane coupler of styryl；3- methacryloyloxypropyl methyls dimethoxysilane, 3- first
Base acryloxypropyl trimethoxy silane, 3- methacryloyloxypropyl methyls diethoxy silane, 3- metering systems
Acryloxypropylethoxysilane triethoxysilane etc. has the silane coupler of methylacryloyl；3- acryloxypropyl trimethoxies
Silane etc. has the silane coupler of acryloyl group；N-2- (amino-ethyl) -3- amino propyl methyls dimethoxysilane, N-2-
(amino-ethyl) -3- TSL 8330s, N-2- (amino-ethyl)-APTES, 3- ammonia
Base propyl trimethoxy silicane, APTES, 3- triethoxysilyls-N- (1,3- dimethyl-Asia
Butyl (butylidene)) propylamine, N- phenyl -3- TSL 8330s, N- (ethylene benzyl) -2- amino-ethyls -
3- TSL 8330s etc. have the silane coupler of amino；3- urea propyl-triethoxysilicanes etc. have urea groups
Silane coupler；3- mercapto hydroxypropyl methyls dimethoxysilane, 3- mercaptopropyl trimethoxysilanes etc. have the silane coupled of sulfydryl
Agent；Double (triethoxysilylpropyltetrasulfide) four thioethers etc. have the silane coupler of thioether group；The second of 3- isocyanates propyl group three
TMOS etc. has the silane coupler of NCO；Silane coupler with carboxyl；With the silane coupled of aldehyde radical
Agent etc..
As the combination for forming compound of the compound of the 1st conversion zone with forming the 2nd conversion zone, preferably have at one end
Amino and there is the silane coupler of siloxanes key in the other end, with there is epoxy radicals at one end and there is siloxanes in the other end
The combination of the silane coupler of key.Wherein, due to the surface on the surface of device substrate 12 and Obstruct membrane 16, silane coupler
Integration density increases, therefore more preferably N-2- (amino-ethyl) -3- TSL 8330s and 3- glycidoxypropyls
The combination of propyl trimethoxy silicane.
Do not have in the method for the 1st conversion zone of formation of device substrate 12 and in the method for the 2nd conversion zone of formation of Obstruct membrane 16
It is particularly limited to.
For example, exemplifying following manner：By making the compound of the conversion zone of composition the 1st be bonded with device substrate, and make structure
Into the compound and the surface bond of Obstruct membrane 16 of the 2nd conversion zone, the 1st conversion zone and the 2nd conversion zone are consequently formed.Wherein, it is excellent
The common film build method such as rubbing method, infusion process, vapour deposition method was gated, at the junction surface as device substrate 12 and Obstruct membrane 16
18 region forms conversion zone.
In addition, the 1st conversion zone and the 2nd conversion zone are substantially only formed at the engagement as device substrate 12 and Obstruct membrane 16
The region in portion 18 is composition surface, but it is also possible in scope the 1st conversion zone of formation more than junction surface 18 and/or the 2nd reaction
Layer.
It has been observed that in the organic el device 10 of the present invention, apart from nearest organic of device substrate 12 in junction surface 18
The distance between the surface of layer 26 and device substrate 12 are below 100nm.In other words, the thickness of the inorganic layer 28 in junction surface 18
Below 100nm is added up to the thickness at junction surface 18.
Junction surface 18 is thinner, more can suppress the intrusion of the moisture from junction surface 18.Also, there is organic layer in substrate
26 inorganic layer 28 becomes thicker, becomes lower to the tracing ability on the surface of organic layer 26, i.e. the flatness on surface becomes lower.
Therefore, if between the surface of organic layer 26 nearest apart from device substrate 12 in junction surface 18 and device substrate 12
Distance more than 100nm, then can produce junction surface become blocked up and uncomfortable situation that moisture is easily invaded and inorganic layer 28 it is flat
Smooth property is deteriorated and the uncomfortable situation of at least one of uncomfortable situation of bonding force step-down in junction surface 18, it is impossible to obtains having and makees
For the organic el device 10 in the life-span of target.If in addition, the surface of the nearest organic layer 26 of distancing element substrate 12 and element base
The distance between plate 12 is more than 100nm, then can cause the flexibility of organic el device 10 also reduces.
If considering this point, the preferably surface of the nearest organic layer 26 of the distancing element substrate 12 in junction surface 18 and element
The distance between substrate 12 is below 75nm, more preferably below 50nm.
In the organic el device 10 of the present invention, the width w at junction surface 18 according to the size of organic el device 10, form the
The species of the compound of 1 conversion zone and the 2nd conversion zone is bonding force between compound, the formation material of device substrate 12
Material, formation material of inorganic layer 28 etc. and the width w of sufficient bonding force can be obtained at junction surface 18 by suitably setting.
Specifically, the preferably width w at junction surface 18 is more than 0.5mm, more preferably more than 1mm.By by junction surface
18 width w is set to more than 0.5mm, and the bonding force at junction surface 18 can be made stronger.
Also, it is preferred that the width w at junction surface 18 is below 5mm, more preferably below 2mm.By by the width at junction surface 18
Degree w is set to below 5mm, and the significant surface of the organic el devices such as display surface and light-emitting area 10 can be ensured extensively.
In the organic el device 10 of the present invention, the sky of device substrate 12 and Obstruct membrane 16 can formed as needed
Between fill the liquid that will not be impacted to organic EL element 14 etc..
By the way that with this structure, in flexible organic el device 10, organic EL can be such as prevented in bending
The damage of element 14.
Also, in the organic el device 10 of the present invention, organic EL element 14 and Obstruct membrane 16 can also be bonded.The situation
Under, preferably organic EL element 14 has on negative electrode by silicon nitride or aluminum oxide formed by sputtering or plasma CVD etc.
Deng inoranic membrane.
As long as the bonding of organic EL element 14 and Obstruct membrane 16 will not be to the performance of organic el device 10 and organic EL members
The bonding that part 14 is impacted, it is possible to use use various methods known to method of adhesive etc..Particularly preferably having
Machine EL element 14 with the opposed faces of Obstruct membrane 16 sets identical with the 1st conversion zone of device substrate 12 and with the of Obstruct membrane 16
Between the conversion zone that 2 conversion zones react, and conversion zone and the 2nd conversion zone of Obstruct membrane 16 by organic EL element 14
React to bond organic EL element 14 and Obstruct membrane 16.As long as in addition, it is arranged on conversion zone and the barrier of organic EL element 14
The conversion zone that 2nd conversion zone of film 16 reacts, then can be by the 1st conversion zone identical conversion zone shape with device substrate 12
Into can also be formed by different conversion zones.
When bonding organic EL element 14 with Obstruct membrane 16, the bonding of the two can be the entire surface of organic EL element 14,
It can also be a part.
Another example of the organic el device of the present invention is shown in Fig. 2.
Organic el device 30 shown in Fig. 2 is also provided with covering Obstruct membrane 16 in the organic el device 10 shown in Fig. 1
The end seal 32 of end and attaching components substrate 12 and Obstruct membrane 16.
By setting this end seal 32, more reliably maintain the molecular bond in junction surface 18 and prevent moisture
Intrusion, can obtain the longer organic el device 30 of service life.Also, in the organic el device 30 of the present invention, in Obstruct membrane
16 end (end face) exposes organic layer 26.Therefore, end seal 32 is bonded in Obstruct membrane 16 with high adhesion, therefore from
This point considers, also can more reliably maintain the molecular bond in junction surface 18.
As one, the use of end seal 32 can bond Obstruct membrane 16 with the adhesive of device substrate 12 to be formed i.e.
Can.Also, by with the high material formation end seal 32 of gas barrier property, can suitably suppress organic EL as caused by moisture
The deterioration of element 14, so as to obtain the longer organic el device 30 of service life.
As the formation material of this end seal 32, the strip materials such as aluminium foil strip, epoxy can be exemplified as one
Curing adhesive of liquid etc. as system or acrylic acid series.
The width abutted with Obstruct membrane 16 of end seal 32 and end seal 32 are abutted with device substrate 12
Width suitably sets the width for the molecular bond being able to maintain that in junction surface 18 i.e. according to formation material of end seal etc.
Can.
In addition, in organic el device 30, when the extraction face of the light from organic EL element 14 is 16 side of Obstruct membrane, being
Widen the significant surface of organic el device 30, preferably end seal 32 by will not reach than junction surface 18 more in the inner part in the way of
Formed.
In addition, end seal 32 covers at least a portion of the end of Obstruct membrane 16 and formed, but preferred covering
The complete cycle of the end of Obstruct membrane 16 and formed.
More than, the organic el device to the present invention is illustrated in detail, but the present invention is not limited to above-mentioned example,
In the range of not departing from spirit of the invention, it is of course possible to carry out various improvement and change.
Embodiment
Hereinafter, the specific embodiment of the present invention is enumerated, the present invention is illustrated in more detail.
[embodiment 1]
The making ＞ of ＜ Obstruct membranes
PET film (TOYOBO CO., LTD. system, A4300) is prepared as supporter 24.
Determined using AFM (SII Nano Technology Inc. systems) in the range of 10 × 10 μm
The surface roughness Ra of supporter 24, is as a result 7.6nm.
It is prepared for TMPTA (Daicel-Cytec.Company, Ltd. system), silane coupler (Shin-Etsu
Chemical Co., Ltd.s system, KBM-5103) and polymerism acid compound (Nippon Kayaku Co., Ltd.s system,
KARAMER PM-21), by quality ratio, with 14.1:3.5:1 composition being obtained by mixing.
By said composition 18.6g, polymerizable ultraviolet initiator (LAMBERTI company systems, ESACURE KTO46) 1.4g and
2- butanone 180g is mixed, so as to be prepared for the coating for forming organic layer 26.
By the coatings prepared in the surface for the supporter 24 (PET film) being ready for.Using bar, to apply thickness
Degree has carried out the coating of coating as 5 μm of mode.
After coating is coated with, coating is dried by placing at room temperature.
Then, by nitrogen displacement method, oxygen concentration is being set to irradiate the ultraviolet of high-pressure mercury-vapor lamp in 0.1% chamber
(accumulative exposure about 1J/cm2), it thus have cured the composition of coating.Thus, thickness is formd on the surface of supporter 24
1000nm ± 50nm organic layer 26.
Thickness 35nm silicon nitride film is formd on the organic layer 26 and as inorganic layer 28.
The formation of inorganic layer 28 (silicon nitride film) is come using common CCP (capacitance coupling plasma mode)-CVD device
Carry out.Unstrpped gas has used silane gas (flow 160sccm), ammonia gas (flow 370sccm), hydrogen (flow
590sccm) and nitrogen (flow 240sccm).Film pressure is set to 40Pa.Power supply has used the high frequency that frequency is 13.56MHz
Power supply, plasma exciatiaon power is set to 2.5kW.
Thus, produce has organic layer 26 and with inorganic layer 28, organic with 1 group thereon on supporter 24
Layer 26 and the Obstruct membrane of the combination of inorganic layer 28.
The formation ＞ of the conversion zones of ＜ the 1st
As device substrate 12, the Obstruct membrane that will be produced before has been used to be cut into the substrate of square configuration.With phase before
The surface roughness Ra of the inorganic layer 28 on the surface of device substrate 12 is determined together, is as a result 0.64nm.
Laminated film (Sun A.Kaken Co., Ltd.s system, PAC-3-50THK) is cut into square configuration, and with only by member
Mask has been made in the mode that the element forming part of part substrate 12 is all covered.It is dilute using pure water in the surface spin coating of device substrate 12
The silane coupler (Shin-Etsu Chemical Co., Ltd.s system, KBE-402) of 2w% concentration is interpreted into, and at 115 DEG C
Dried in baking oven 1 hour.Mask has been peeled off after drying.Thus, the device substrate 12 for being formed with the 1st conversion zone is produced.
The making ＞ of ＜ organic EL elements
On the surface for the device substrate 12 (inorganic layer 28) for being formed with the 1st conversion zone, in the way of the thickness as 60nm
Vacuum evaporation Al, so as to form anode.In the anode surface formed, by vacuum deposition apparatus, formed with 2nm thickness
MoO3Layer and as hole injection layer, in addition, in MoO3The surface of layer successively with 29nm thickness evaporation hole transmission layer (α-
NPD：Double [N- (1- naphthyls)-N- phenyl] benzidine) (Bis [N- (1-naphthyl)-N-phenyl] benzidine)), with
20nm thickness is deposited CBP (double (carbazole -9- bases) biphenyl (4,4'-Bis (carbazol-9-yl) biphenyl) of 4,4'-)
As main material and be doped with 5% Ir (ppy)3((three (2- phenylpyridines) close iridium) (Tris (2-phenylpyridinato)
Iridium luminescent layer)), with 10nm thickness evaporation BAlq (double-(2- methyl -8-hydroxyquinoline) -4- (phenyl-phenol) -
Aluminium (III) (Bis- (2-methyl-8-quinolinolato) -4- (phenyl-phenolate)-aluminium (III)))
Layer and as hole blocking layer, with 20nm thickness evaporating Al q3 (three (8- Hydroxy-quinolins) aluminium (Tris (8-hydroxy-
Quinolinato) aluminium)) layer and as electron transfer layer, so as to form organic electro luminescent layer.
Then, it is deposited successively with 0.5nm thickness evaporation LiF, with 1.5nm thickness on the surface of gained organic luminous layer
Al, the thickness evaporation Ag with 15nm, so as to form transparency electrode (negative electrode) film, and form organic EL on the surface of device substrate 12
Element 14.
The formation ＞ of the conversion zones of ＜ the 2nd
Compared with the laminated film used when forming 1 conversion zone, Obstruct membrane is cut in the way of 1 side increase 4mm
Into square configuration.
Spin coating is diluted to the silane coupler of 2w% concentration using pure water in the entire surface on the surface of Obstruct membrane
(Shin-Etsu Chemical Co., Ltd.s system, KBE-903), and dried 1 hour in 115 DEG C of baking oven, so as to form the
2 conversion zones.
The making ＞ of ＜ organic el devices 10
The inorganic layer 28 on face and Obstruct membrane surface of organic EL element 14 will be formed as opposed face, and it is organic to cover
The mode of EL element makes Obstruct membrane fit on device substrate 12.Now, by by the center pair of device substrate 12 and Obstruct membrane
It is accurate and fit, form junction surfaces 18 of the width w for 2mm.
Then, to press the state of the 1st conversion zone and the 2nd conversion zone, 2 hours are stood in 80 DEG C of baking oven, is made the 1st anti-
Layer is answered to be reacted with the 2nd conversion zone, so as to be bonded device substrate 12 and Obstruct membrane.Thus, produce by junction surface 18
Attaching components substrate 12 and Obstruct membrane, and seal by Obstruct membrane the organic el device of organic EL element 14.
In addition, after performance evaluation as shown below is carried out, junction surface 18 is shot using scanning electron microscope
Section, so as to determine the distance between device substrate 12 and the nearest organic layer 26 of distancing element substrate 12.As a result, element
The distance between substrate 12 and the nearest organic layer 26 of distancing element substrate 12 are 48nm.
[embodiment 2]
When making Obstruct membrane, by being also identically formed organic layer 26 on inorganic layer 28, and on the organic layer 26
Inorganic layer 28 is identically formed, so as to produce combination, the as shown in Figure 3 resistance with 2 groups of organic layers 26 Yu inorganic layer 28
Barrier film 16.
The Obstruct membrane 16 has been used as device substrate 12, and organic EL element 14 is sealed by the Obstruct membrane 16,
In addition, the organic el device 10 shown in Fig. 1 is produced in the same manner as example 1.
In addition, determining the result of the surface roughness Ra of Obstruct membrane 16, rough surface in the same manner as example 1
Degree Ra is 0.47nm.I.e., in the present example, the surface roughness Ra of device substrate 12 is 0.47nm.
Also, nearest organic of device substrate 12 and distancing element substrate 12 is determined in the same manner as example 1
Layer the distance between 26, is as a result 41nm.
[embodiment 3]
Cover the complete cycle of the end of Obstruct membrane 16 and form the end across the end of Obstruct membrane 16 and device substrate 12
Seal 32, in addition, produces the organic el device 30 shown in Fig. 2 in the same way as in example 2.
By along the end of Obstruct membrane 16 be coated with epoxy adhesive (Nagase ChemteX Corporation systems,
XNR5516Z), protection foil element surface is used, and 6000mJ/cm is turned into accumulative exposure2Mode illumination wavelength 356nm
Ultraviolet and make the adhesive solidify, be consequently formed end seal 32.
[comparative example 1]
In addition to without organic layer 26, Obstruct membrane same as Example 1 is produced.That is, the Obstruct membrane is in support
Only there is one layer of inorganic layer 28 on body 24.In addition, determining the surface roughness of Obstruct membrane 16 in the same manner as example 1
Ra result, surface roughness Ra is 5.3nm.I.e., in the present example, the surface roughness Ra of device substrate 12 is 5.3nm.
In addition to using the Obstruct membrane, organic el device is produced in the same manner as example 1.
[comparative example 2]
Device substrate has been carried out using epoxy adhesive (Nagase ChemteX Corporation systems, XNR5516Z)
12 with the engagement of Obstruct membrane, in addition, organic el device is produced in the same manner as example 1.By along connecing
Conjunction portion 18 is coated with after adhesive, superimposed elements substrate 12 and Obstruct membrane, and turns into 6000mJ/cm with accumulative exposure2's
Mode illumination wavelength 356nm ultraviolet and solidify adhesive, thus engaged.
Determine in the same manner as example 1 device substrate 12 and the nearest organic layer 26 of distancing element substrate 12 it
Between distance, be as a result 510nm.
[performance evaluation]
＜ bond strengths ＞
In entire surface the 1st conversion zone of formation of device substrate 12, and the 2nd conversion zone is formed in the entire surface of Obstruct membrane, not
Make element and them is fitted.Afterwards, 2 hours are stood in 80 DEG C of baking oven and promotes reaction.It is disposed at stretching
The stripping for determining 180 ° of directions in testing machine (SHIMADZU CORPORATION systems, Autograph AG-Xplus) is strong
Degree.
In addition, in embodiment 3, bond strength is determined as follows.That is, formd in the entire surface of device substrate 12
1st conversion zone.On the other hand, Obstruct membrane is cut out relative to device substrate 12 in the way of end reduces 2mm, and in entire surface
Form the 2nd conversion zone.Then, do not form element and device substrate is fitted with Obstruct membrane, it is afterwards, quiet in 80 DEG C of baking oven
Put 2 hours and promote reaction.In addition, epoxy adhesive is coated with along the side of the end of Obstruct membrane 3, to add up exposure
As 6000mJ/cm2Mode illumination wavelength 356nm ultraviolet and make the adhesive solidify, be consequently formed end seal.
1 avris that this is never carried out to end part seal is peeled off and determines peel strength now.
Also, in comparative example 2, device substrate 12 entire surface be coated with epoxy adhesive, superimposed elements substrate 12 with
Obstruct membrane, 6000mJ/cm is turned into accumulative exposure2Mode illumination wavelength 356nm ultraviolet and solidify adhesive, by
This makes the device substrate 12 be fitted with Obstruct membrane.
＜ element durability ＞
The organic el device produced placed 100 hours in the environment of 60 DEG C, relative humidity 90%.
Apply 7V's using the SMU2400 types source measuring unit (Source Measure Unit) of Keithley company systems
Voltage and make the organic EL device after placement light, using micro- sem observation light-emitting area, so as to the dim spot relative to light-emitting area
The gross area evaluated.
The gross area of dim spot is evaluated as " A " less than 10%,
The gross area of dim spot is evaluated as " B " for 10~50%,
By the gross area of dim spot being evaluated as " C " more than 50%.
＜ bending strengths ＞
In entire surface the 1st conversion zone of formation of device substrate 12, and the 2nd conversion zone is formed in the entire surface of Obstruct membrane, not
Make element and them is fitted.Afterwards, 2 hours are stood in 80 DEG C of baking oven and promotes reaction.
In embodiment 3, identically with bond strength, in entire surface the 1st conversion zone of formation of device substrate 12, and obstruct
Film is cut out relative to device substrate 12 in the way of end reduces 2mm, and in entire surface the 2nd conversion zone of formation, does not form element
And device substrate is fitted with Obstruct membrane.Afterwards, 2 hours are stood in 80 DEG C of baking oven and promotes reaction.In addition, along resistance
The side coating epoxy adhesive of end 4 of barrier film, 6000mJ/cm is turned into accumulative exposure2Mode illumination wavelength 356nm
Ultraviolet and make the adhesive solidify, be consequently formed end seal.
Also, in comparative example 2, device substrate 12 entire surface be coated with epoxy adhesive, superimposed elements substrate 12 with
Obstruct membrane, and 6000mJ/cm is turned into accumulative exposure2Mode illumination wavelength 356nm ultraviolet and solidify adhesive,
Thus the device substrate 12 is made to be fitted with Obstruct membrane.
By this according to JIS-K5600-5-1, bending strength is determined by bent spindle testing machine.In addition, result is shown
Peeling-off maximum mandrel diameters.Also, observe by the naked eye and confirm to peel off.
Result above is shown in following tables.
[table 1]
Only embodiment 3 has end seal
As shown in the above Table, according to the present invention, obtain in junction surface 18 by molecular bond, member is bonded with high adhesion
Part substrate 12 and Obstruct membrane 16, service life length and flexible also excellent organic el device.
In contrast, the Obstruct membrane without organic layer has been used as in the comparative example 1 of device substrate, device substrate
Surface roughness Ra is higher, as rise thus junction surface bonding force it is insufficient, the generating element substrate 12 in junction surface 18
With the stripping of Obstruct membrane 16 etc., it is impossible to obtain sufficient element durability.
Also, in the engagement that device substrate 12 and Obstruct membrane 16 are carried out using epoxy adhesive, and device substrate 12
With distancing element substrate 12 in the long comparative example 2 of the distance between nearest organic layer 26, it is believed that immerse moisture from junction surface
And cause organic EL element 14 to deteriorate, fail to obtain sufficient element durability.Also, with the bonding using common adhesive
Compare, the thinner thickness of adhesive, therefore bond strength and bending strength are also insufficient.
According to result above, effect of the invention is obvious.
Industrial applicability
It can preferably use in organic el display or organic EL illuminating.
Symbol description
10th, the organic EL of 30- (organic electroluminescent) device, 12- device substrates, the organic EL of 14- (organic electroluminescent) members
Part, 16- (gas) Obstruct membrane, 18- junction surfaces, 24- supporters, 26- organic layers, 28- inorganic layers, 32- end seals.
Claims (9)
1. a kind of Organnic electroluminescent device, it is characterised in that have：Device substrate；Organic electroluminescent device, is formed at institute
State device substrate；And gas barrier film, cover the organic electroluminescent device and engage and have described in sealing with the device substrate
Electro-luminescence element,
In the gas barrier film, there is more than 1 group of inorganic layer and the organic layer of the substrate as the inorganic layer on supporter
Combination, surface is inorganic layer, and the inorganic layer on the surface is engaged towards the device substrate,
The device substrate and gas barrier film are engaged through the reaction between the 1st conversion zone and the 2nd conversion zone to carry out, and described
1 conversion zone is arranged on the device substrate, and the 2nd conversion zone is arranged on the gas barrier film and is bonded with the 1st conversion zone,
In the junction surface of the device substrate and gas barrier film, the organic layer and element base nearest apart from the device substrate
The distance between plate is below 100nm.
2. Organnic electroluminescent device according to claim 1, wherein,
The surface roughness Ra in the formation organic layer of the supporter and the face of inorganic layer is below 30nm.
3. Organnic electroluminescent device according to claim 1 or 2, wherein,
The thickness for being formed at the organic layer on the surface of the supporter is more than 0.1 μm.
4. Organnic electroluminescent device according to any one of claim 1 to 3, wherein,
The end of the gas barrier film is by adhesive coverage.
5. Organnic electroluminescent device according to any one of claim 1 to 4, wherein,
The surface roughness Ra in the face of the formation organic electroluminescent device of the device substrate is below 5nm.
6. Organnic electroluminescent device according to any one of claim 1 to 5, wherein,
The width at the junction surface is 0.5~5mm.
7. Organnic electroluminescent device according to any one of claim 1 to 6, wherein,
The thickness of the inorganic layer is 10~45nm.
8. Organnic electroluminescent device according to any one of claim 1 to 7, wherein,
The device substrate is following gas barrier film, and the gas barrier film has more than 1 group of inorganic layer with turning into institute on supporter
The combination and surface for stating the organic layer of the substrate of inorganic layer are inorganic layer,
Inorganic layer on the surface forms the organic electroluminescent device.
9. Organnic electroluminescent device according to any one of claim 1 to 8, wherein,
1st conversion zone contains silane coupler, and the 2nd conversion zone contains and the silane contained by the 1st conversion zone
The silane coupler that coupling agent reacts,
By the reaction between the silane coupler of the 1st conversion zone and the silane coupler of the 2nd conversion zone, the member is carried out
The engagement of part substrate and gas barrier film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-036937 | 2015-02-26 | ||
| JP2015036937A JP6383682B2 (en) | 2015-02-26 | 2015-02-26 | Organic electroluminescence device |
| PCT/JP2016/052750 WO2016136389A1 (en) | 2015-02-26 | 2016-01-29 | Organic electroluminescence apparatus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107251649A true CN107251649A (en) | 2017-10-13 |
Family
ID=56788365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680009199.1A Pending CN107251649A (en) | 2015-02-26 | 2016-01-29 | Organnic electroluminescent device |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6383682B2 (en) |
| KR (1) | KR101917552B1 (en) |
| CN (1) | CN107251649A (en) |
| WO (1) | WO2016136389A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20210066660A1 (en) * | 2018-03-28 | 2021-03-04 | Sakai Display Products Corporation | Organic electroluminescent display device and method for producing same |
| CN111886928A (en) * | 2018-03-28 | 2020-11-03 | 堺显示器制品株式会社 | Organic EL display device and method for manufacturing the same |
| US20210202913A1 (en) * | 2018-05-18 | 2021-07-01 | Corning Incorporated | Light extraction apparatus and flexible oled displays |
| JP6620277B1 (en) * | 2018-08-07 | 2019-12-18 | 株式会社豊光社 | Method for producing plated glass substrate |
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- 2015-02-26 JP JP2015036937A patent/JP6383682B2/en not_active Expired - Fee Related
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- 2016-01-29 KR KR1020177022115A patent/KR101917552B1/en active IP Right Grant
- 2016-01-29 WO PCT/JP2016/052750 patent/WO2016136389A1/en active Application Filing
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| JP2009038003A (en) * | 2007-07-11 | 2009-02-19 | Dainippon Printing Co Ltd | Gas barrier sheet, sealing body and organic el display |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2016162485A (en) | 2016-09-05 |
| WO2016136389A1 (en) | 2016-09-01 |
| KR20170101306A (en) | 2017-09-05 |
| KR101917552B1 (en) | 2018-11-09 |
| JP6383682B2 (en) | 2018-08-29 |
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