CN104103660A - OLED (organic light emitting diode) display packaged by composite thin film and manufacturing method thereof - Google Patents
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Abstract
The invention discloses an OLED (organic light emitting diode) display packaged by a composite thin film and a manufacturing method thereof. The OLED display comprises a substrate main body, an OLED function layer formed on the substrate main body, a moisture adsorption layer formed on the substrate main body and covering the OLED, a first inorganic barrier layer formed on the substrate main body and covering the moisture adsorption layer, a first flexible transition buffer layer formed between the moisture adsorption layer and the first inorganic barrier layer, a second inorganic barrier layer formed on the substrate main body and covering the first inorganic barrier layer, and a first flexible transition buffer layer formed between the first barrier layer and the second inorganic barrier layer. The flexible transition buffer layer has both high water-blocking characteristics of an inorganic matter and flexible characteristics of an organic matter, the residual stress problem between the inorganic material barrier layers can be avoided, and the chance that steam enters the OLED can be greatly reduced. The invention also discloses a manufacturing method of the OLED (organic light emitting diode) display.
Description
Technical field
The invention belongs to a kind of Organic Light Emitting Diode (OLED) display and manufacture method thereof, be specifically related to a kind of OLED display and manufacture method thereof of thin-film package.
Background technology
Organic electroluminescent LED (Organic light emitting diode, OLED) be called again display of organic electroluminescence, its structure belongs to sandwich type structure, conventionally anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and negative electrode etc., consisting of, is a kind of total solids display that utilizes current drives.Under the driving of impressed current, electronics and holoe carrier are injected into leads organic luminous layer, then in luminescent layer, is compounded to form exciton, by exciton radiation de excitation, is sent out and luminous.Because OLED has frivolous, power saving, wide viewing angle, image quality is even, reaction speed is fast, can realize the features such as flexible demonstration, be acknowledged as " dreamlike display ".
Yet OLED is a kind of to steam and the extremely responsive device of oxygen, as long as the not encapsulation of OLED device just easily cause stain at light-emitting zone, and stain can expand along with the time.On the one hand, penetrate into the steam of device and oxygen can with the metal material of the low work function of device cathodes, such as Al, Mg, Ca etc., there is oxidation reaction, cause forming insulating barrier at negative electrode and organic functions interlayer, cause the device cannot be luminous.Meanwhile, during the work of OLED device, the existence of steam can be brought out the electrolysis venting that electrochemical reaction and water occur between anode and negative electrode, forms blackspot.On the other hand, also can there is irreversible chemical reaction with steam, oxygen in organic material, destroys the stability of organic molecule, reduces device luminous efficiency.Therefore, significant to extending device lifetime in order to protect OLED to avoid the impact of steam and oxygen.
Tradition OLED makes electrode and organic function layer in the rigid substrate such as glass, metal, the encapsulation that this class device is carried out is generally to add a rigid cover plate to device, in cover plate inner side, stick enough drying sheets, and the gap of substrate and cover plate is solidified to reach sealing effectiveness with epoxy resin UV.Yet the shortcoming of rigid cover plate encapsulation is that device volume and weight after encapsulation are too large, cannot realize the flexible OLED encapsulation of the formula of can having mercy on.In order to address these problems, patent CN102569678A is a kind of like this method openly, covers successively MgF in OLED functional layer
2, ZnS or MgF
2/ ZnS film is the laminated film encapsulating structure as resilient coating as pre-packaged layer, translucent silica and silicon nitride, to reach moisture-vapor transmission (WVTR) lower than 10
-6g/m
2the object of day.Patent CN201010105368.6 further discloses a kind of like this method, adopt calcium oxide to do moisture absorbed layer, high-temperature ceramic materials is done respectively as the first secondary retention layer, the first barrier layer, the second secondary retention layer, the second barrier layer, and moisture absorbed layer and each barrier layer cover on OLED negative electrode successively.Yet these method for packing also have shortcoming, because inorganic thin film material and glass substrate difference in thermal coefficient of expansion and Young's modulus is generally all very large, it is larger that device is lighted the stress that expanded by heating produces, easily stress problem and being damaged.For example, glass, SiO
2and Al
2o
3thermal coefficient of expansion (10
-6/ K) and Young's modulus (GPa) be respectively 8.3 and 82.0,0.5 and 86.9,4.45 and 58.9, can cause residual excessive stress between silica and aluminum oxide film and glass substrate, finally cause device package to lose efficacy.
Above-mentioned in background disclosed information be only used to strengthen the understanding to background technology of the present invention, therefore, it may comprise the information that is not formed in this domestic prior art well known by persons skilled in the art.
Summary of the invention
Main purpose of the present invention is to provide organic light emitting display and the manufacture method thereof of a laminated film encapsulation, to address the above problem.
Shortcoming for above-mentioned prior art, the present invention has disclosed a kind of organic light emitting display of laminated film encapsulation, described OLED display comprises base main body, in described base main body, form OLED functional layer, in described base main body, form and cover the moisture absorption layer of OLED, with the first inorganic barrier layer that forms and cover described moisture absorption layer in described base main body, between described moisture absorption layer and described the first inorganic barrier layer, form and cover described the first flexible transition resilient coating, in described base main body, form and cover the second inorganic barrier layer of described the first inorganic barrier layer, and the second flexible transition resilient coating forming between described the first barrier layer and described the second inorganic barrier layer.Flexible transition resilient coating of the present invention is with high water resistant characteristic and the organic flexible feature of inorganic matter, can there is good toughness and adhesion on the one hand, to reduce the residual excessive stresses of film, there is on the other hand good water vapor rejection ability, to avoid steam, oxygen or other gas to destroy organic luminous layer in organic light emitting display or the physical characteristic of other internal structures, to cause device efficiency to roll-off and component life reduces.
The present invention also provides a kind of manufacture method of organic light emitting display of laminated film encapsulation.
An organic light emitting diode display for laminated film encapsulation, comprising: base main body, has a plurality of Organic Light Emitting Diodes on described substrate; Organic Light Emitting Diode, described Organic Light Emitting Diode is formed in described base main body; And being positioned at the laminated film encapsulated layer on described substrate, described laminated film encapsulated layer covers on described a plurality of organic illuminating element; Moisture absorption layer, described moisture absorption layer is formed in described base main body and covers described Organic Light Emitting Diode; The first barrier layer, described the first barrier layer is formed in described base main body and covers described moisture absorption layer; The first flexible transition resilient coating, described the first flexible transition resilient coating is formed between described moisture absorption layer and described the first barrier layer; The second barrier layer, described the second barrier layer is formed in described base main body and covers described the first barrier layer; And the second flexible transition resilient coating, described the second flexible transition resilient coating is formed between described the first barrier layer and described the second barrier layer.
Described moisture absorption layer can form film by vacuum thermal evaporation technique in organic light emitting diode display, and thin-film material can comprise that a kind of material in free barium monoxide, a calcium oxide, silicon monoxide, magnesium oxide and their group constituting forms.
The Organic Light Emitting Diode of described laminated film encapsulation, each freely comprises and selects free SiO to it is characterized in that described the first barrier layer and the second barrier layer
2, Al
2o
3, ZrO, TiO
2, AlON, SiON, ZnO, Ta
2o
5, a kind of material in AlN and their group constituting forms, can be formed by chemical vapour deposition (CVD) (PECVD) or the atomic layer deposition method (ALD) of plasma strengthening separately.
Described the first barrier layer and the second barrier layer can be covered and be formed by the inorganic material differing from one another.
The interface formation of the first described flexible transition resilient coating between the first described barrier layer and described moisture absorption layer.Described the second flexible transition resilient coating is by the interface formation between the second barrier layer described and described the first barrier layer.
Described the first flexible transition resilient coating and the second flexible transition resilient coating are hybridized polymer film, described hybridized polymer is selected from one or both materials that form in tetramethylsilane (TMS) polymer, tetraethoxysilane (TEOS) polymer, SiOxCy and their combination and forms, wherein preferred tetraethoxysilane (TEOS) polymer.
Described hybridized polymer film can form by the chemical vapour deposition (CVD) (PECVD) of the plasma strengthening that is presoma for tetramethylsilane (TMS) monomer, tetraethoxysilane (TEOS) monomer, SiOxCy monomer.
The Organic Light Emitting Diode of described laminated film encapsulation, it is characterized in that described moisture absorption layer, described the first flexible transition resilient coating, the first described barrier layer, described the second flexible transition resilient coating and described the second barrier layer form the thin-film encapsulation layer of the described Organic Light Emitting Diode of protection, and the integral thickness of described thin-film encapsulation layer is in the scope of 100～5000nm, flexible transition buffer layer thickness should be equal to or greater than barrier layer thickness, effectively to eliminate inorganic layer stress and covering absorbent layer, the defect occurring in the first barrier layer or the second barrier layer, and form smooth thin layer.
Accompanying drawing explanation
In conjunction with the drawings exemplary embodiment is described in detail, feature will become obviously to those skilled in the art, in accompanying drawing:
Fig. 1 illustrates the OLED sectional view according to exemplary embodiment;
Fig. 2 illustrates laminated film encapsulation process figure, and wherein 1 is substrate, and 2 is OLED functional layer, and 3 is moisture absorption layer, and 4 is the first flexible transition resilient coating, and 5 is the first barrier layer, and 6 is the second flexible transition resilient coating, and 7 is the second barrier layer.
Fig. 3 illustrates the interface of laminated film encapsulated layer.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further:
Embodiment 1.
Please refer to Fig. 1, Fig. 1 is organic light emitting display 110 midship section schematic diagrames of the present invention.As shown in Figure 1, organic light emitting display 400 includes a substrate 100, OLED200 and a laminated film protective layer structure 300 and is covered on organic light emitting display OLED200 and substrate 100, to avoid OLED element 200 to be exposed in external environment.Laminated film protective layer 300 is included in the upper moisture absorption layer 310 that covers and form of OLED200; cover the first flexible transition resilient coating 320 forming on moisture absorption layer 310; cover the first barrier layer 330 forming on the first flexible transition resilient coating 320; the second flexible transition resilient coating 340 of the interface formation between the first barrier layer 330 and the second barrier layer 350, and the second barrier layer 350.
Please refer to Fig. 2, Fig. 2 is the procedure chart of laminated film encapsulation.As shown in Figure 2, on substrate 1, by vacuum thermal evaporation, prepare OLED thin-film material 2 and cover the moisture absorption layer 3 on OLED2, chemical vapour deposition technique PECVD by plasma strengthening forms the first flexible transition resilient coating 4 and the second flexible transition resilient coating 6 on described moisture absorption layer 3, then by atomic layer deposition method ALD, on described flexible transition resilient coating, forms the first barrier layer 5 and the second barrier layer 7.The interface formation of described the first flexible transition resilient coating 4 between described moisture absorption layer 3 and the first barrier layer 5, described the second flexible transition resilient coating 6 is at the first described flexible transition resilient coating 5 and the interface formation between the second barrier layer 7.
Embodiment 2.
Please refer to Fig. 3, Fig. 3 is the surface chart of laminated film encapsulated layer 300.As shown in Figure 3; laminated film protective layer 300 is included in the upper moisture absorption layer 310 that covers and form of OLED200; cover the first flexible transition resilient coating 320 forming on moisture absorption layer 310; cover the first barrier layer 330 forming on the first flexible transition resilient coating 320; the second flexible transition resilient coating 340 of the interface formation between the first barrier layer 330 and the second barrier layer 350, and the second barrier layer 350.
Moisture absorption layer 310 covers on oled layer, absorbs the steam that is penetrated into organic light emitting display inside, the life-span of protection display.A kind of material in the optional free barium monoxide of moisture absorption layer 310, a calcium oxide, silicon monoxide, magnesium oxide and their group constituting forms by thermal evaporation technique, preferably vacuum thermal evaporation technique.
The first flexible transition resilient coating 320 and the second flexible transition resilient coating 340 are by comprising that at least one or two materials in free tetramethylsilane (TMS) monomer, tetraethoxysilane (TEOS) monomer, SiOxCy monomer and their group constituting form.Now, the first flexible transition resilient coating 320 and the second flexible transition resilient coating can be formed by the material differing from one another.
The first flexible transition resilient coating 320 and the second flexible transition resilient coating 340 form above-mentioned thin-film material by the chemical vapour deposition (CVD) (PECVD) of plasma strengthening.Consider the organic material of protection OLED200, the first flexible transition resilient coating 320 and the second flexible transition resilient coating 340 should 100 ℃ with interior process conditions under chemical vapour deposition technique (PECVD) by plasma strengthening form thin layer.The first flexible transition resilient coating 320 and the second flexible transition resilient coating 340 have toughness and the adhesion of organic material on the one hand, can effectively eliminate the residual stress of other inorganic thin film layers, and adhere on inorganic thin film.On the other hand, the first flexible transition resilient coating 320 and the second flexible transition resilient coating 340 have the characteristic of part inorganic material, can play the effect of certain obstruct steam.As described in Figure 3, the first flexible transition resilient coating 320 and the second flexible transition resilient coating 340 form smooth thin layer, fill the defect in the first barrier layer or the second barrier layer, effectively to intercept steam.
The first barrier layer 330 and the second barrier layer 350 freely comprise and select free SiO
2, Al
2o
3, ZrO, TiO
2, AlON, SiON, ZnO, Ta
2o
5, at least one material in AlN and their group constituting forms.The first barrier layer 330 and the second barrier layer 350 can be formed by chemical vapour deposition (CVD) (PECVD) or the atomic layer deposition method (ALD) of plasma strengthening separately, preferably atomic layer deposition method (ALD).Now, the first barrier layer 330 and the second barrier layer 350 are piled up and are formed by highdensity inorganic material, can effectively suppress the infiltration of steam and oxygen.
Embodiment 3.
Use mechanical pump to be evacuated to 10-
2torr, then open condenser pump until temperature is down to 11K, use condenser pump to be extracted into high vacuum 10
-6after torr, the moisture absorption layer 310 that starts to prepare OLED device 200 and cover OLED200 on the substrate 100 cleaning up.Organic matter vaporization plating in OLED200 is controlled at
left and right, prevents that subliming type material local heating from spraying suddenly pollution cavity, and affects thickness.Negative electrode in OLED200 keeps at the beginning
speed evaporation
avoid the flatness of hot metal material impact damage organic layer, after, evaporation speed can be controlled at
with the complete residue cathode thickness of interior evaporation.Moisture absorption layer 310 can form film by a kind of material in barium monoxide, a calcium oxide, silicon monoxide, magnesium oxide and their group constituting in the temperature of not damaging OLED200.The evaporation rate of above material and thickness adopt quartz crystal to carry out the film thickness of Real-Time Monitoring OLED200 and moisture absorption layer 310.
The first flexible transition resilient coating 320 and the second flexible transition resilient coating 340 are by comprising that at least one material in free tetramethylsilane (TMS) polymer, tetraethoxysilane (TEOS) polymer, SiOxCy polymer and their group constituting forms.Now, the first flexible transition resilient coating 320 and the second flexible transition resilient coating can be formed by the material differing from one another.For example, utilizing tetraethoxysilane (TEOS) is monomer, and chemical vapour deposition (CVD) (PECVD) formation that cooperation is carried out plasma enhancing containing oxygen plasma contains [(C
2h
5o)
2-Si-O] the flexible transition buffer layer thin film of tetraethoxysilane (TEOS) polymerization of n construction unit.In processing procedure, can utilize different speed (Air flow) to adjust deposition rate and the second best in quality film morphology of material.For example, when Air Flow is controlled at 10sccm, film deposition rate is 4.31nm/s, and surface roughness is 0.9996; When Air Flow is controlled at 50sccm, film deposition rate is 2.63nm/s, and surface roughness is 0.9962.
The first barrier layer 330 and the second barrier layer 350 comprise and select free SiO
2, Al
2o
3, ZrO, TiO
2, AlON, SiON, ZnO, Ta
2o
5, at least one material in AlN and their group constituting forms.The first barrier layer 330 and the second barrier layer 350 can be formed by the Plasma Enhanced Chemical Vapor Deposition (PECVD) of strengthening (PECVD) or atomic layer deposition method (ALD), preferably atomic layer deposition method (ALD).For example, in order not damage OLED200, by atomic layer deposition method (ALD), form the first barrier layer 330 and the second barrier layer 350 films, film should be grown under the process conditions lower than 100 degrees Celsius.
The integral thickness of thin-film package protective layer 300 is in 100nm～5000nm, and flexible transition resilient coating and barrier layer should be controlled rational thickness.When flexible transition buffer layer thickness should be equal to or greater than the thickness of barrier layer, can play the residual stress of good elimination inorganic material, and adhere in inorganic material.When the thickness of flexible transition resilient coating is much smaller than barrier layer thickness, be not only difficult to play the object that eliminates stress, and cannot intercept steam.In addition, flexible transition layer thickness is greater than the defect that inorganic layer effectively occurs in covering absorbent layer, the first barrier layer or the second barrier layer and forms smooth thin layer, enters the chance of device to reduce steam.
The laminated film encapsulated layer 300 of the organic light emitting display 400 of the laminated film encapsulation by above-mentioned structure has lower than 10
-6g/m
2it moisture-vapor transmission (WVTR) and low OTR oxygen transmission rate (OTR).
Although in conjunction with thinking at present the illustrative embodiments that can put into practice, the present invention is described in detail, but be understood that, the invention is not restricted to the execution mode of announcing, on the contrary, the present invention is intended to covering and comprises various modifications and equivalents within the scope of the appended claims.
Claims (13)
1. the organic light emitting diode display that laminated film encapsulates, comprising:
Base main body, has a plurality of Organic Light Emitting Diodes on described substrate;
Organic Light Emitting Diode, described Organic Light Emitting Diode is formed in described base main body;
And being positioned at the laminated film encapsulated layer on described substrate, described laminated film encapsulated layer covers on described a plurality of organic illuminating element;
Moisture absorption layer, described moisture absorption layer is formed in described base main body and covers described Organic Light Emitting Diode;
The first barrier layer, described the first barrier layer is formed in described base main body and covers described moisture absorption layer;
The first flexible transition resilient coating, described the first flexible transition resilient coating is formed between described moisture absorption layer and described the first barrier layer;
The second barrier layer, described the second barrier layer is formed in described base main body and covers described the first barrier layer;
And the second flexible transition resilient coating, described the second flexible transition resilient coating is formed between described the first barrier layer and described the second barrier layer.
2. organic light emitting diode display according to claim 1, is characterized in that described moisture absorption layer is by comprising that a kind of material in free barium monoxide, a calcium oxide, silicon monoxide, magnesium oxide and their group constituting forms.
3. organic light emitting diode display according to claim 1 and 2, wherein said moisture absorption layer material forms by thermal evaporation technique.
4. the Organic Light Emitting Diode of laminated film according to claim 1 encapsulation, each freely comprises and selects free SiO to it is characterized in that described the first barrier layer and the second barrier layer
2, Al
2o
3, ZrO, TiO
2, AlON, SiON, ZnO, Ta
2o
5, a kind of material in AlN and their group constituting forms.
5. the Organic Light Emitting Diode of laminated film encapsulation according to claim 1, is characterized in that described the first barrier layer and the second barrier layer can be formed by chemical vapour deposition (CVD) (PECVD) or the atomic layer deposition method (ALD) of plasma strengthening separately.
6. the Organic Light Emitting Diode of laminated film encapsulation according to claim 1, is characterized in that described the first barrier layer and the second barrier layer are covered and formed by the inorganic material differing from one another.
7. the Organic Light Emitting Diode of laminated film according to claim 1 encapsulation, is characterized in that the interface formation of the first described flexible transition resilient coating between the first described barrier layer and described moisture absorption layer.
8. the Organic Light Emitting Diode of laminated film according to claim 1 encapsulation, is characterized in that described the second flexible transition resilient coating is by the interface formation between the second barrier layer described and described the first barrier layer.
According to claim according to the flexible transition resilient coating described in claim 7 and 8, it is characterized in that described the first flexible transition resilient coating and the second flexible transition resilient coating are hybridized polymer film, described hybridized polymer is selected from one or both materials that form in tetramethylsilane (TMS) polymer, tetraethoxysilane (TEOS) polymer, SiOxCy and their combination and forms, wherein preferred tetraethoxysilane (TEOS) polymer.
10. tetraethoxysilane according to claim 9 (TEOS) polymer, is characterized in that containing [(C
2h
5o)
2-Si-O] n construction unit.
The Organic Light Emitting Diode of 11. laminated film encapsulation according to claim 1, wherein said flexible transition resilient coating forms by the chemical vapour deposition (CVD) (PECVD) of plasma strengthening, and precursor gas is selected from tetramethylsilane (TMS) monomer, tetraethoxysilane (TEOS) monomer or SiOxCy monomer.
The Organic Light Emitting Diode of 12. laminated film encapsulation according to claim 1, it is characterized in that described moisture absorption layer, described the first flexible transition resilient coating, the first described barrier layer, described the second flexible transition resilient coating and described the second barrier layer form the thin-film encapsulation layer of the described Organic Light Emitting Diode of protection, and the integral thickness of described thin-film encapsulation layer is in the scope of 100～5000nm, flexible transition buffer layer thickness should be equal to or greater than barrier layer thickness, effectively to eliminate inorganic layer stress and covering absorbent layer, the defect occurring in the first barrier layer or the second barrier layer, and form smooth thin layer.
The manufacture method of the display of the Organic Light Emitting Diode of 13. 1 kinds of laminated film encapsulation, comprising:
By vacuum thermal evaporation method, on base main body, be formed with successively the moisture absorption layer of OLED and the described Organic Light Emitting Diode of covering;
By plasma fortified chemical vapour deposition technique or atomic layer deposition method, form the first barrier layer and the second barrier layer that covers described moisture absorption layer;
Interface formation the first flexible transition resilient coating by plasma fortified chemical vapour deposition technique between described the first barrier layer and described moisture absorption layer; With
By plasma fortified chemical vapour deposition technique the second described barrier layer and and described the first barrier layer between the second flexible transition resilient coating of interface formation.
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