CN103187533B - A kind of organic electroluminescence device and preparation method thereof - Google Patents
A kind of organic electroluminescence device and preparation method thereof Download PDFInfo
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- CN103187533B CN103187533B CN201110456045.6A CN201110456045A CN103187533B CN 103187533 B CN103187533 B CN 103187533B CN 201110456045 A CN201110456045 A CN 201110456045A CN 103187533 B CN103187533 B CN 103187533B
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Abstract
The present invention relates to a kind of organic electroluminescence device and preparation method thereof, organic electroluminescence device includes the following layers stacked gradually: substrate, the first electrode layer, organic function layer, the second electrode lay, and, it also includes one layer of low-refraction grid layer, the refractive index of described grid layer is more than 1.0 and is less than the refractive index of described organic function layer, described grid layer is placed between the first electrode layer and organic function layer, or described grid layer is placed between substrate and the first electrode layer.By the regulation to beam path of this grid layer, make part originally and arrive in air because the light beam of total reflection loss is injected into glass, thus improve brightness and the efficiency of organic light emitting display.
Description
Technical field
The present invention relates to a kind of organic electroluminescence device (Organic Light Emitting Device, the most also letter
Claim OLED), particularly relate to a kind of organic electroluminescence device comprising grid layer.The invention still further relates to described organic electroluminescent
The preparation method of device.
Background technology
OLED possesses multiple structure, including substrate, anode layer, organic function layer and cathode layer.Substrate is generally by refractive index
Material less than 1.7 makes (refractive index of such as glass substrate is generally 1.4～1.5) and the refraction of organic function layer thereon
Rate is generally 1.7～1.8.Therefore, there is significant portion of light beam at the organic function layer of high index and relatively low-refraction
Interface between substrate occurs total reflection to be limited in organic function layer, it is impossible to injects substrate and arrives in air, so that
The light that OLED is actually sent out in air only about 20%, and have the light of about 80% to be confined or be lost at device inside, it is impossible to
It is removed application.Want to obtain high brightness, high efficiency OLED, it is necessary to the light output efficiency of OLED is greatly improved.
US20040119402 describes by by substrate manufacture trapezoidal shape and at trapezoidal top making groove, inciting somebody to action
OLED is produced on wherein, so that being confined in organic layer, injecting to the light beam substrate by trapezoidal shape of device side
Arrive substrate front surface, thus improve efficiency and the brightness of device.But this method simply takes out the light beam of device marginal portion,
And the substrate shape of this structure is complicated, makes difficulty, cost of manufacture is high.
CN1498046A describes one layer of light scattering layer of addition between glass substrate and the first electrode layer, makes at organic layer
And change light path by scattering due to the light beam that is limited in organic layer of total reflection between glass substrate interface, make part light
Bundle enters glass substrate and arrives in air, improves efficiency and the brightness of device.But this method also makes originally can enter glass
The light beam of substrate is limited in organic layer owing to scattering changes light path, and this method entirety improves device efficiency or the ratio of brightness
Example is relatively low, simultaneously because scattering layer complicated process of preparation, actual application value is the highest.
CN1571595B describes addition light loss inside OLED and prevents layer and microgap layer.Wherein, light loss is prevented
Only layer is made up of with protruding diffraction grating multiple；Microgap layer is filled by gas or vacuum and is formed.But due to diffraction grating
Fineness requires higher, and therefore manufacturing process is complicated, and yield rate is low.And device inside insufflation gas will produce product and stablize
Sex chromosome mosaicism and the problem such as ruggedness is undesirable, homogeneity of product is poor.
Summary of the invention
It is an object of the present invention to provide a kind of light output performance with improvement and easily prepared organic light emission shows
Show device.
The organic light emitting display of the present invention includes the following layers stacked gradually: substrate, the first electrode layer, organic functions
Layer, the second electrode lay, and, it also includes one layer of low-refraction grid layer, and the refractive index of described grid layer is more than 1.0 and low
In the refractive index of described organic function layer, described grid layer is between the first electrode layer and organic function layer, or described grid
Compartment is between substrate and the first electrode layer.
The present invention also provides for the preparation method of described organic light emitting display, is included on substrate and forms described low refraction
Rate grid layer, is then sequentially depositing the first electrode layer, organic function layer and the second electrode lay being laminated to each other；Or on substrate
Deposition of first electrode layer, forms low-refraction grid layer on the first electrode layer, is then sequentially depositing the organic merit being laminated to each other
Ergosphere and the second electrode lay；Then encapsulate.
The organic light emitting display of the present invention, by comprising described low-refraction grid layer, makes a part original organic
The light beam that functional layer is lost because of total reflection reason with substrate interface, by this low-refraction grid layer tune to beam path
Joint, and be injected in substrate thus arrive in air.Therefore, the organic light emitting display of the present invention have raising brightness and
Efficiency.And owing to this low-refraction grid layer is less demanding to processing technique fineness, therefore can by simple technique such as
Photoetching process makes, and good product consistency.
Accompanying drawing explanation
Fig. 1 is the profile of the structure (comparative example 1) of organic light emitting display in prior art；
Fig. 2 is comparative example 1 light emitting pixel graphic diagram；
Fig. 3 is the square grid layer pattern of embodiment 1；
Fig. 4 is the square grid pattern demonstrated in the pixel region of embodiment 1；
Fig. 5 is the profile of a kind of OLED structure of the present invention；
Fig. 6 is the profile of another kind OLED structure of the present invention；
Fig. 7 is the comb mesh pattern of the nested shape of the square demonstrated in pixel region；
Fig. 8 is the comb mesh pattern of the hexagonal nests shape demonstrated in pixel region；
Fig. 9 is the comb mesh pattern of the circular nested shape demonstrated in pixel region；
Figure 10 is the interior hexagonal grid pattern arranged with tight adjacent fashion of single pixel region；
Figure 11 is the hexagonal grid pattern arranged with tight adjacent fashion shown in pixel region.
Detailed description of the invention
The organic light emitting display of the present invention includes the following layers stacked gradually: substrate, the first electrode layer, organic functions
Layer, the second electrode lay, and, it also includes one layer of low-refraction grid layer, and the refractive index of described grid layer is more than 1.0 and low
In the refractive index of described organic function layer, described grid layer is between the first electrode layer and organic function layer, or described grid
Compartment is between substrate and the first electrode layer.
Described grid layer can have described refractive index with any and be applicable to the material of OLED and make, for the ease of thereon
Form comb mesh pattern, it is preferred to use photoresist prepares the insulation of described grid layer, such as contact panel photonasty and protective layer light
Resist EOC130.
In order to enable more light to inject substrate and to arrive in air, the most described grid layer is positioned at substrate and the first electricity
Between the layer of pole.
The refractive index of this grid layer is preferably 1.0-1.5.The refractive index of grid layer is the lowest, enters into substrate and arrives in air
Light beam the most, display device brightness improve amplitude the biggest.
In order to make more to inject substrate via the light of grid layer regulation light path and enter in air, preferably this grid layer
Light transmittance is 75%-99%.
For ease of making, the preferably thickness of this grid layer is 0.1 μm～20 μm, more preferably 0.1 μm～5 μm.
In each pixel region, the pattern that the bossing of described grid layer is constituted is preferably: with tight adjacent fashion
(the most each all adjacent with other n-shaped of n-shaped not being positioned at most peripheral is total to the n-shaped of multiple formed objects of arrangement
Use each limit) so that grid layer pattern is netted, and wherein each limit of n-shaped is bossing；Or it is a series of with concentric form
Layer by layer nested shape is identical and multiple n-shapeds that size is different or circle, wherein within the border of each pixel region,
Region area beyond maximum n-shaped or circle is preferably greater than 0 and not higher than 1/4 with the ratio of this pixel region gross area.Its
Middle N >=3, and described n-shaped is preferably equilateral triangle, square or regular hexagon.
In the width on each limit of the above-mentioned n-shaped arranged with tight adjacent fashion or above-mentioned pattern nested layer by layer
The width d1 of each maximum n-shaped or circular interior each bossing is preferably 0.05 μm～20 μm, above-mentioned tight arranged adjacent
N-shaped cellular grid in the positive N of each maximum in the circumradius in each n-shaped space or pattern nested layer by layer
The width d2 in limit shape or circular interior each space (not including the space in bosom) is preferably 1 μm～30 μm, the sky in described bosom
The preferably smaller than maximum n-shaped of the width of gap or circular in two times of other each gap length d2.The size of d1 and d2 affects device
The brightness of part.In order to improve the brightness of device, d1 is more preferably 0.05 μm to 5 μm, and especially 0.05 μm is to 3 μm, and d2 is more preferably
It is that 1 μm is to 10 μm.
Described grid layer region beyond pixel region can have comb mesh pattern, it is possible to does not have comb mesh pattern and whole
As bossing.
Described OLED can have insulating barrier and insulated column layer forms to define pixel region, described insulating barrier and insulated column layer
It is laminated to each other and between grid layer and organic function layer or between the first electrode layer and organic function layer.But, work as institute
Stating when not having comb mesh pattern in grid layer part beyond pixel region, described OLED can not comprise additionally in described insulation
Layer.Insulating barrier and insulated column layer can use in this area and be conventionally used for making insulating barrier and the material of insulated column layer and method system
Make, use photoetching process to make the most with photoresist.
In described OLED, the first transparent electrode layer can be used and possess the second electrode lay of reflection function, it is possible to adopting
With possessing the first electrode layer of reflection function and transparent the second electrode lay, or use the first transparent electrode layer and transparent
The second electrode lay.
In embodiments herein, in the first electrode layer and the second electrode lay, any one can be anode, and another one is cloudy
Pole, and the material being conventionally used for manufacturing electrode layer can be used to prepare, such as ITO (tin indium oxide) or Ag or Al.
Organic function layer generally includes hole transmission layer, luminescent layer and electron transfer layer, and it all can use in prior art
Prepared by the material being usually used in manufacturing these layers.As the material of hole transmission layer, such as arylamine class material low molecule material can be used
Material etc., such as N, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1 '-xenyl-4,4 '-diamidogen (NPB)；As electric transmission
The material of layer, can use such as metal organic complex, aromatic condensed ring class or o-phenanthroline class etc., such as three (8-hydroxyquinolines)
Aluminum (Alq3).Luminescent layer can be made up of the material that commonly used in the art for luminescent layer, such as can by luminescent layer material of main part and send out
Photosphere dyestuff forms.Luminescent layer material of main part can use in this area the material being conventionally used for this purpose, such as small molecule material
Such as metal organic complex, carbazole derivates, anthracene derivant etc., such as 9,10-bis-(naphthalene-2-base) anthracene (ADN).Luminescent layer dyestuff
The material being conventionally used for this purpose can be used in this area, such as, contain atomic number at least one atom more than 36 less than 84
Compound or derivant, such as 2,5,8,11-tetra-terts (TBPe).Luminescent layer material of main part and the ratio of luminescent layer dyestuff
Example can use its conventional ratio in the art.
It addition, described organic function layer also can farther include hole injection layer and/or electron injecting layer, hole injection layer
The material being usually used in hole injection layer or electron injecting layer all can be used in prior art with electron injecting layer.Hole injection layer material
Material can be such as m-MTDATA, and electron injecting layer material can be such as LiF.
The thickness of above layers all can use its general thickness in OLED.
Fig. 5 illustrates the profile of a kind of OLED structure of the present invention.Wherein, 10 is substrate；20 is the first electrode layer；30 is low
Refractive index grid layer；40 is organic function layer, it may include hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer；50
For the second electrode lay.
Fig. 6 illustrates the profile of another kind device architecture of the present invention.Wherein, 10 is substrate；30 is grid layer；20 is first
Electrode layer；40 is organic function layer, it may include hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer；50 is second
Electrode layer.
The preparation of the organic light emitting display of the present invention is included on substrate and forms described low-refraction grid layer, then
It is sequentially depositing the first electrode layer, organic function layer and the second electrode lay being laminated to each other；Or deposition of first electrode on substrate
Layer, forms low-refraction grid layer on the first electrode layer, is then sequentially depositing the organic function layer being laminated to each other and the second electricity
Pole layer；Then encapsulate.
Described grid layer can such as be prepared by photoetching process, or by other any appropriate methodologies well known by persons skilled in the art
Preparation.When described grid layer is prepared by photoetching process, its preparation process specifically includes that and is coated with on substrate or on the first electrode layer
There is the photoresist of described refractive index；Dry；The mask with desirable pattern is used to be exposed；And development.
Described deposition can use well known by persons skilled in the art can by the inventive method desired substance cover at whole mesh
Any suitable method on mark surface, such as vacuum vapour deposition.Encapsulation can use any appropriate well known by persons skilled in the art
Method.
By the following examples the present invention is further described.Wherein brightness silicon photo diode is measured.Each enforcement
In example, the refractive index of the low-refraction grid layer formed is identical with the refractive index of the material for forming it.
Comparative example 1
With ITO electro-conductive glass as substrate, etching ITO the first electrode pattern, wherein ITO thickness is 200nm, passes through photoetching
Method prepares the insulating barrier and insulated column layer that thickness is 1-3 μm so that pixel size is 0.28mm × 0.28mm.This ITO is conducted electricity
Glass substrate is put in evaporation chamber, and during evaporation, chamber pressure is less than 5.0 × 10-3Pa.First evaporation 40nm thickness N, N '-
Two-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4,4 '-diamidogen (NPB) is as hole transmission layer；The side steamed altogether with double source
Thick for method evaporation 30nm 9,10-bis-(naphthalene-2-base) anthracene (ADN) and 2,5,8,11-tetra-terts (TBPe) are as luminescent layer, logical
Crossing rate controlled TBPe ratio in ADN is 7%；Three (8-hydroxyquinoline) aluminum (Alq of evaporation 20nm3) as electric transmission
Layer；The LiF of evaporation 0.5nm as the Al of electron injecting layer and 150nm as the second electrode lay.
Fig. 1 is the profile of comparative example 1 device architecture.Wherein, 10 is substrate；20 is the first electrode layer ITO；40 is organic
Functional layer, including hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer；50 is the second electrode lay.
Fig. 2 is the light emitting pixel graphic diagram of comparative example 1.
Embodiment 1:
With the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode pattern, prepare thereon
One layer of low-refraction grid layer, thickness about 2 μm.Low-refraction grid preparation process is as follows: spin coating layer of transparent light in ITO pattern
Photoresist (contact panel photonasty insulation and protective layer photoresist EOC130, light transmittance is more than 80%, and refractive index is 1.5).Dry
After Gan, select the mask of continuous print square net figure anyway with 150mj/cm2Light exposure exposure；Life with above-mentioned photoresist
The developing liquid developing that business men provides simultaneously obtain after 100 seconds special pattern (square net, d1 as hereinbefore defined and is 1 μm,
D2 as hereinbefore defined and is 8 μm) grid layer.Prepare insulating barrier and insulated column layer thereon identically with comparative example 1 so that
Pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with hole transmission layer, luminescent layer, electric transmission successively
Layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10-3Pa, first evaporation 40nm thickness NPB is made
For hole transmission layer；TBPe is controlled as luminescent layer, through-rate using ADN and TBPe thick for method evaporation 30nm that double source steams altogether
Ratio in ADN is 7%；The Alq of evaporation 20nm3As electron transfer layer；The LiF of evaporation 0.5nm is as electron injecting layer
With the Al of 150nm as the second electrode lay.
Fig. 3 is the grid layer pattern of embodiment 1；
Fig. 4 is the comb mesh pattern demonstrated in the pixel region of embodiment 1；
Embodiment 2:
With the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode pattern, prepare thereon
One layer of low-refraction grid layer, thickness about 2 μm.Low-refraction grid preparation process is as follows: spin coating layer of transparent light in ITO pattern
Photoresist (photoresist same as in Example 1, light transmittance is more than 80%, and refractive index is 1.5).After drying, select square grid anyway
The mask of trrellis diagram shape is with 150mj/cm2Light exposure exposure；Special pattern is obtained in the same manner as in Example 1 after development
The grid layer of (square net similar to Example 1, d1 is 0.05 μm, and d2 is 1 μm).Thereon identically with comparative example 1
Prepare insulating barrier and insulated column layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with sky successively
Cave transport layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation chamber pressure less than 5.0 ×
10-3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；Make with ADN and TBPe thick for method evaporation 30nm that double source steams altogether
For luminescent layer, it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3As electron transfer layer；Evaporation
The LiF of 0.5nm as the Al of electron injecting layer and 150nm as the second electrode lay.
Embodiment 3:
With the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode pattern, prepare thereon
One layer of low-refraction grid layer, thickness about 2 μm.Low-refraction grid preparation process is as follows: spin coating layer of transparent light in ITO pattern
Photoresist (photoresist same as in Example 1, light transmittance is more than 80%, and refractive index is 1.5).After drying, select square grid anyway
The mask of trrellis diagram shape is with 150mj/cm2Light exposure exposure；Special pattern is obtained in the same manner as in Example 1 after development
The grid layer of (square net similar to Example 1, but d1 is 1 μm, d2 is 4 μm).Make thereon identically with comparative example 1
Standby insulating barrier and insulated column layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with hole successively
Transport layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10- 3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；ADN and TBPe thick for method evaporation 30nm steamed altogether using double source as
Luminescent layer, it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3As electron transfer layer；Evaporation
The LiF of 0.5nm as the Al of electron injecting layer and 150nm as the second electrode lay.
Embodiment 4:
With the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode pattern, prepare thereon
One layer of low-refraction grid layer, thickness about 2 μm.Low-refraction grid preparation process is as follows: spin coating layer of transparent light in ITO pattern
Photoresist (photoresist same as in Example 1, light transmittance is more than 80%, and refractive index is 1.5).After drying, select square grid anyway
The mask of trrellis diagram shape is with 150mj/cm2Light exposure exposure；Special pattern is obtained in the same manner as in Example 1 after development
The grid layer of (square net similar to Example 1, d1 is 1 μm, and d2 is 2 μm).Prepare thereon identically with comparative example 1
Insulating barrier and insulated column layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with successively hole pass
Defeated layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10- 3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；ADN and TBPe thick for method evaporation 30nm steamed altogether using double source as
Luminescent layer, it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3As electron transfer layer；Evaporation
The LiF of 0.5nm as the Al of electron injecting layer and 150nm as the second electrode lay.
Embodiment 5:
With the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode pattern, prepare thereon
One layer of low-refraction grid layer, thickness about 2 μm.Low-refraction grid preparation process is as follows: spin coating layer of transparent light in ITO pattern
Photoresist (photoresist same as in Example 1, light transmittance is more than 80%, and refractive index is 1.5).After drying, select square grid anyway
The mask of trrellis diagram shape is with 150mj/cm2Light exposure exposure；Special pattern is obtained in the same manner as in Example 1 after development
The grid layer of (square net similar to Example 1, d1 is 8 μm, and d2 is 25 μm).Make thereon identically with comparative example 1
Standby insulating barrier and insulated column layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with hole successively
Transport layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10- 3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；ADN and TBPe thick for method evaporation 30nm steamed altogether using double source as
Luminescent layer, it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3As electron transfer layer；Evaporation
The LiF of 0.5nm as the Al of electron injecting layer and 150nm as the second electrode lay.
Embodiment 6:
With clear glass as substrate, prepare one layer of low-refraction grid layer, thickness about 2 μm thereon.Low-refraction grid layer
Preparation process is as follows: on substrate substrate, (photoresist same as in Example 1, light transmittance is more than spin coating layer of transparent photoresist
80%, refractive index is 1.5).After drying, select the mask of square net figure anyway with 150mj/cm2Light exposure exposure；With
(square net similar to Example 1, d1 is 1 μm, and d2 is 4 to obtain special pattern after method development same as in Example 1
μm) grid layer.On grid layer, using ITO the first electrode layer that direct current magnetron sputtering process prepares 150nm, ITO target is
Indium stannum alloy, its component ratio In: Sn=90%: 10%.In preparation process, partial pressure of oxygen is 0.4Sccm, and argon partial pressure is 20Sccm.
After preparing ITO layer, lithographic method is used to etch ito anode.Prepare insulating barrier and isolation thereon identically with comparative example 1
Post layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with successively hole transmission layer, luminescent layer,
Electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10-3Pa, is first deposited with
40nm thickness NPB is as hole transmission layer；ADN and TBPe thick for method evaporation 30nm steamed altogether using double source, as luminescent layer, passes through
Rate controlled TBPe ratio in ADN is 7%；The Alq of evaporation 20nm3As electron transfer layer；The LiF of evaporation 0.5nm makees
For the Al of electron injecting layer and 150nm as the second electrode.
Embodiment 7:
With the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode pattern, prepare thereon
One layer of low-refraction grid layer, thickness about 2 μm.Low-refraction grid preparation process is as follows: spin coating layer of transparent light in ITO pattern
Photoresist (photoresist same as in Example 1, light transmittance is more than 80%, and refractive index is 1.5).After drying, select the most square embedding
The mask of the figure of shell-like is with 150mj/cm2Light exposure exposure；Specific pattern is obtained in the same manner as in Example 1 after development
Shape (in each pixel region a series of multiple foursquare grids nested layer by layer with concentric form, the most each pixel
Largest square in region is identical with pixel region size, and d1 is 1 μm, and d2 is 4 μm) grid layer.Thereon with comparative example 1
Prepare insulating barrier and insulated column layer in the same manner so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in successively
Evaporation hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than
5.0×10-3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；The ADN thick for method evaporation 30nm that steams altogether with double source and
TBPe is as luminescent layer, and it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3As electric transmission
Layer；The LiF of evaporation 0.5nm as the Al of electron injecting layer and 150nm as the second electrode lay.
Fig. 7 is the comb mesh pattern of the nested shape of square of the pixel region of embodiment 7.
Embodiment 8:
With clear glass as substrate, prepare one layer of low-refraction grid layer, thickness about 2 μm thereon.Low-refraction grid layer
Preparation process is as follows: on substrate substrate, (photoresist same as in Example 1, light transmittance is more than spin coating layer of transparent photoresist
80%, refractive index is 1.5).After drying, select the mask of the most square nested shape figure with 150mj/cm2Light exposure exposure；
Special pattern (figure similar to Example 7, d1 is 1 μm, and d2 is 4 μm) is obtained in the same manner as in Example 1 after development
Grid layer.On grid layer, using ITO the first electrode layer that direct current magnetron sputtering process prepares 150nm, ITO target is indium
Ashbury metal, its component ratio In: Sn=90%: 10%.In preparation process, partial pressure of oxygen is 0.4Sccm, and argon partial pressure is 20Sccm.System
After going out ITO the first electrode layer, lithographic method is used to etch ITO the first electrode.Prepare thereon absolutely identically with comparative example 1
Edge layer and insulated column layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with hole transport successively
Layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10-3Pa,
First evaporation 40nm thickness NPB is as hole transmission layer；It is deposited with ADN and TBPe thick for 30nm as luminescence using the method that double source steams altogether
Layer, it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3As electron transfer layer；Evaporation 0.5nm
LiF as the Al of electron injecting layer and 150nm as the second electrode lay.
Embodiment 9:
With clear glass as substrate, prepare one layer of low-refraction grid layer, thickness about 2 μm thereon.Low-refraction grid layer
Preparation process is as follows: on substrate substrate, (photoresist same as in Example 1, light transmittance is more than spin coating layer of transparent photoresist
80%, refractive index is 1.5).After drying, select the mask of anti-hexagonal nests shape figure with 150mj/cm2Light exposure exposure；
Special pattern is obtained in the same manner as in Example 1 (a series of with concentric form layer in each pixel region after development
Multiple hexagonal grid that layer is nested, in the most each pixel region, the spacing of maximum hexagonal two parallel edges is equal to picture
The element region length of side, d1 is 1 μm, and d2 is 4 μm) grid layer.On grid layer, direct current magnetron sputtering process is used to prepare 150nm
ITO the first electrode layer, ITO target is indium stannum alloy, its component ratio In: Sn=90%: 10%.Partial pressure of oxygen in preparation process
For 0.4Sccm, argon partial pressure is 20Sccm.After preparing ITO the first electrode layer, lithographic method is used to etch ITO the first electrode.
Prepare insulating barrier and insulated column layer thereon so that pixel size is 0.28mm × 0.28mm identically with comparative example 1.After put into
Evaporation chamber is deposited with hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay successively.Evaporation process
Middle chamber pressure is less than 5.0 × 10-3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；The method evaporation steamed altogether with double source
ADN and TBPe thick for 30nm is as luminescent layer, and it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3
As electron transfer layer；The LiF of evaporation 0.5nm as the Al of electron injecting layer and 150nm as the second electrode lay.
Fig. 8 is the comb mesh pattern of the hexagonal nests shape of the pixel region of embodiment 9.
Embodiment 10:
With clear glass as substrate, prepare one layer of low-refraction grid layer, thickness about 2 μm thereon.Low-refraction grid layer
Preparation process is as follows: on substrate substrate, (photoresist same as in Example 1, light transmittance is more than spin coating layer of transparent photoresist
80%, refractive index is 1.5).After drying, select the mask of anti-circular nested shape figure with 150mj/cm2Light exposure exposure；With
Obtain after method development same as in Example 1 special pattern (in each pixel region a series of with concentric form layer by layer
The grid of nested multiple circles, the greatest circle in the most each pixel region is inscribed within pixel region, and d1 is 1 μm, and d2 is 4 μ
M) grid layer.On grid layer, using ITO the first electrode layer that direct current magnetron sputtering process prepares 150nm, ITO target is
Indium stannum alloy, its component ratio In: Sn=90%: 10%.In preparation process, partial pressure of oxygen is 0.4Sccm, and argon partial pressure is 20Sccm.
After preparing ITO the first electrode layer, lithographic method is used to etch ITO the first electrode.Prepare thereon identically with comparative example 1
Insulating barrier and insulated column layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with successively hole pass
Defeated layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10- 3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；ADN and TBPe thick for method evaporation 30nm steamed altogether using double source as
Luminescent layer, it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3As electron transfer layer；Evaporation
The LiF of 0.5nm as the Al of electron injecting layer and 150nm as the second electrode lay.
Fig. 9 is the comb mesh pattern of the circular nested shape of the pixel region of embodiment 10.
Embodiment 11:
With the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode pattern, prepare thereon
One layer of low-refraction grid layer, thickness about 2 μm.Low-refraction grid layer preparation process is as follows: spin coating layer of transparent in ITO pattern
Photoresist (light transmittance is more than 80%, and refractive index is 1.3).After drying, select the mask of square net figure anyway with 150mj/
cm2Light exposure exposure；Special pattern (square similar to Example 1 is obtained in the same manner as in Example 1 after development
Grid, d1 is 1 μm, and d2 is 4 μm) grid layer.Prepare insulating barrier and insulated column layer thereon identically with comparative example 1 so that
Pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with hole transmission layer, luminescent layer, electric transmission successively
Layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10-3Pa, first evaporation 40nm thickness NPB is made
For hole transmission layer；TBPe is controlled as luminescent layer, through-rate using ADN and TBPe thick for method evaporation 30nm that double source steams altogether
Ratio in ADN is 7%；The Alq of evaporation 20nm3As electron transfer layer；The LiF of evaporation 0.5nm is as electron injecting layer
With the Al of 150nm as the second electrode lay.
Embodiment 12:
With clear glass as substrate, prepare one layer of low-refraction grid layer, thickness about 2 μm thereon.Low-refraction grid layer
Preparation process is as follows: spin coating layer of transparent photoresist (light transmittance is more than 80%, and refractive index is 1.3) on substrate substrate.Dry
After, select the mask of square net figure anyway with 150mj/cm2Light exposure exposure；Show in the same manner as in Example 1
Movie queen obtains the grid layer of special pattern (square net similar to Example 1, d1 is 1 μm, and d2 is 4 μm).In grid layer
On, using ITO the first electrode layer that direct current magnetron sputtering process prepares 150nm, ITO target is indium stannum alloy, its component ratio
In: Sn=90%: 10%.In preparation process, partial pressure of oxygen is 0.4Sccm, and argon partial pressure is 20Sccm.Prepare ITO the first electrode layer
After, use lithographic method to etch ITO the first electrode.Prepare insulating barrier and insulated column layer thereon identically with comparative example 1, make
Obtaining pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with hole transmission layer, luminescent layer, electric transmission successively
Layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10-3Pa, first evaporation 40nm thickness NPB is made
For hole transmission layer；TBPe is controlled as luminescent layer, through-rate using ADN and TBPe thick for method evaporation 30nm that double source steams altogether
Ratio in ADN is 7%；The Alq of evaporation 20nm3As electron transfer layer；The LiF of evaporation 0.5nm is as electron injecting layer
With the Al of 150nm as the second electrode lay.
Embodiment 13:
With the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode pattern, prepare thereon
One layer of low-refraction grid layer, thickness about 2 μm.Low-refraction grid layer preparation process is as follows: spin coating layer of transparent in ITO pattern
Photoresist (light transmittance is more than 80%, and refractive index is 1.7).After drying, select the mask of square net figure anyway with 150mj/
cm2Light exposure exposure；Special pattern (square similar to Example 1 is obtained in the same manner as in Example 1 after development
Grid, d1 is 1 μm, and d2 is 4 μm) grid layer.Prepare insulating barrier and insulated column layer thereon identically with comparative example 1 so that
Pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with hole transmission layer, luminescent layer, electric transmission successively
Layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10-3Pa, first evaporation 40nm thickness NPB is made
For hole transmission layer；TBPe is controlled as luminescent layer, through-rate using ADN and TBPe thick for method evaporation 30nm that double source steams altogether
Ratio in ADN is 7%；The Alq of evaporation 20nm3As electron transfer layer；The LiF of evaporation 0.5nm is as electron injecting layer
With the Al of 150nm as the second electrode lay.
Embodiment 14:
With the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode pattern, prepare thereon
One layer of low-refraction grid layer, thickness about 2 μm.Low-refraction grid layer preparation process is as follows: spin coating layer of transparent in ITO pattern
Photoresist (photoresist same as in Example 1, light transmittance is more than 80%, and refractive index is 1.5).After drying, select continuous print anti-
The mask of regular hexagonal cell figure is with 150mj/cm2Light exposure exposure；Obtain after development in the same manner as in Example 1
The grid layer of special pattern (regular hexagonal cell, d1 is 1 μm, and d2 is 5 μm).Prepare insulation thereon identically with comparative example 1
Layer and insulated column layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with successively hole transmission layer,
Luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay, during evaporation, chamber pressure is less than 5.0 × 10-3Pa.This reality
Executing in example, first organic layer is deposited with 40nm thickness NPB as hole transmission layer；The ADN thick for method evaporation 30nm steamed altogether with double source
With TBPe as luminescent layer, it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3Pass as electronics
Defeated layer；The LiF of evaporation 0.5nm as the Al of electron injecting layer and 150nm as the second electrode lay.
Figure 10 is the hexagonal grid pattern in the single pixel region of embodiment 14.
Figure 11 is the hexagonal grid pattern of the pixel region of embodiment 14.
Embodiment 15:
With clear glass as substrate, prepare one layer of low-refraction grid layer, thickness about 2 μm thereon.Low-refraction grid layer
Preparation process is as follows: on substrate substrate, (photoresist same as in Example 1, light transmittance is more than spin coating layer of transparent photoresist
80%, refractive index is 1.5).After drying, select the mask of hexagonal mesh figure anyway with 150mj/cm2Light exposure exposure；
In the same manner as in Example 1 development after obtain special pattern (regular hexagonal cell similar to Example 14, d1 is 1 μm,
D2 is 5 μm) grid layer.On grid layer, use ITO the first electrode layer that direct current magnetron sputtering process prepares 150nm, ITO
Target is indium stannum alloy, its component ratio In: Sn=90%: 10%.In preparation process, partial pressure of oxygen is 0.4Sccm, and argon partial pressure is
20Sccm.After preparing ITO layer, lithographic method is used to etch ITO the first electrode.Prepare thereon identically with comparative example 1
Insulating barrier and insulated column layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with successively hole pass
Defeated layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10- 3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；ADN and TBPe thick for method evaporation 30nm steamed altogether using double source as
Luminescent layer, it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3As electron transfer layer；Evaporation
The LiF of 0.5nm as the Al of electron injecting layer and 150nm as the second electrode lay.
Comparative example 2:
With clear glass as substrate, sputtering or evaporation coating method is used to make the silver of one layer of 100nm as the first electricity thereon
Pole.After etching silver-colored first electrode pattern, prepare insulating barrier and insulated column layer thereon so that pixel is big identically with comparative example 1
Little for 0.28mm × 0.28mm.Put into and evaporation chamber is deposited with hole transmission layer, luminescent layer, electron transfer layer, electronics note successively
Enter layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10-3Pa, first evaporation 40nm thickness NPB passes as hole
Defeated layer；ADN and TBPe thick for method evaporation 30nm steamed altogether using double source is as luminescent layer, and through-rate controls TBPe in ADN
Ratio be 7%；The Alq of evaporation 20nm3As electron transfer layer；The Li of evaporation 0.5nm is as electron injecting layer, and rear employing is spattered
Shooting method makes the ITO of 150nm as the second electrode lay.
Embodiment 16:
With clear glass as substrate, sputtering or evaporation coating method is used to make the silver of one layer of 100nm as the first electrode.Etching
After silver the first electrode pattern, prepare one layer of low-refraction grid layer, thickness about 2 μm thereon.Low-refraction grid layer preparation process
As follows: on silver figure, (photoresist same as in Example 1, light transmittance is more than 80% to spin coating layer of transparent photoresist, refractive index
It is 1.5).After drying, select the mask of hexagonal mesh figure anyway with 150mj/cm2Light exposure exposure；With with embodiment 1
Special pattern (regular hexagonal cell similar to Example 14, d1 is 1 μm, and d2 is 5 μm) is obtained after identical method development
Grid layer.Prepare insulating barrier and insulated column layer thereon identically with comparative example 1 so that pixel size be 0.28mm ×
0.28mm.After put into evaporation chamber in be deposited with successively hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, second electricity
Pole layer.During evaporation, chamber pressure is less than 5.0 × 10-3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；With double source
ADN and TBPe thick for method evaporation 30nm steamed altogether is as luminescent layer, and it is 7% that through-rate controls TBPe ratio in ADN；
The Alq of evaporation 20nm3As electron transfer layer；The Li of evaporation 0.5nm is as electron injecting layer, and rear employing sputtering method makes
The ITO of 150nm is as the second electrode lay.
Embodiment 17:
With clear glass as substrate, prepare one layer of low-refraction grid layer, thickness about 2 μm thereon.Low-refraction grid system
Standby process is as follows: on substrate, (photoresist same as in Example 1, light transmittance is more than 80% to spin coating layer of transparent photoresist, folding
The rate of penetrating is 1.5).After drying, select the mask of hexagonal mesh figure anyway with 150mj/cm2Light exposure exposure；With with reality
(regular hexagonal cell similar to Example 14, d1 is 1 μm, and d2 is 5 μ to obtain special pattern after executing the method development that example 1 is identical
M) grid layer.Rear employing sputtering or evaporation coating method make the silver of one layer of 100nm as the first electrode.Etch silver-colored first electrode figure
After shape.Prepare insulating barrier and insulated column layer thereon so that pixel size is 0.28mm × 0.28mm identically with comparative example 1.
Put in evaporation chamber and be deposited with hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay successively.Evaporation
During chamber pressure less than 5.0 × 10-3Pa.In the present embodiment, first organic layer is deposited with 40nm thickness NPB as hole transport
Layer；ADN and TBPe thick for method evaporation 30nm steamed altogether using double source is as luminescent layer, and through-rate controls TBPe in ADN
Ratio is 7%；The Alq of evaporation 20nm3As electron transfer layer；The Li of evaporation 0.5nm, as electron injecting layer, uses sputtering afterwards
Method makes the ITO of 150nm as the second electrode lay.
Comparative example 3:
Using the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode, thereon with contrast
Example 1 prepares insulating barrier and insulated column layer in the same manner so that pixel size is 0.28mm × 0.28mm.Put into and be deposited with in chamber successively
Evaporation hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than
5.0×10-3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；The ADN thick for method evaporation 30nm that steams altogether with double source and
TBPe is as luminescent layer, and it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3As electric transmission
Layer；The Li of evaporation 0.5nm is as electron injecting layer, and the rear ITO using sputtering method to make 150nm is as the second electrode lay.
Embodiment 18:
With the ITO electro-conductive glass identical with comparative example 1 as substrate, after etching ITO the first electrode pattern, prepare thereon
One layer of low-refraction grid layer, thickness about 2 μm.Low-refraction grid preparation process is as follows: spin coating layer of transparent light in ITO pattern
Photoresist (photoresist same as in Example 1, light transmittance is more than 80%, and refractive index is 1.5).After drying, select square grid anyway
The mask of trrellis diagram shape is with 150mj/cm2Light exposure exposure；Special pattern is obtained in the same manner as in Example 1 after development
The grid layer of (square net similar to Example 1, d1 is 1 μm, and d2 is 4 μm).Prepare thereon identically with comparative example 1
Insulating barrier and insulated column layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with successively hole pass
Defeated layer, luminescent layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10- 3Pa, first evaporation 40nm thickness NPB is as hole transmission layer；ADN and TBPe thick for method evaporation 30nm steamed altogether using double source as
Luminescent layer, it is 7% that through-rate controls TBPe ratio in ADN；The Alq of evaporation 20nm3As electron transfer layer；Evaporation
The Li of 0.5nm is as electron injecting layer, and the rear ITO using sputtering method to make 150nm is as the second electrode lay.
Embodiment 19:
With clear glass as substrate, prepare one layer of low-refraction grid layer, thickness about 2 μm thereon.Low-refraction grid layer
Preparation process is as follows: on substrate substrate, (photoresist same as in Example 1, light transmittance is more than spin coating layer of transparent photoresist
80%, refractive index is 1.5).After drying, select the mask of square net figure anyway with 150mj/cm2Light exposure exposure；With
(square net similar to Example 1, d1 is 1 μm, and d2 is 4 to obtain special pattern after method development same as in Example 1
μm) grid layer.On grid layer, using ITO the first electrode layer that direct current magnetron sputtering process prepares 150nm, ITO target is
Indium stannum alloy, its component ratio In: Sn=90%: 10%.In preparation process, partial pressure of oxygen is 0.4Sccm, and argon partial pressure is 20Sccm.
After preparing ITO layer, lithographic method is used to etch ITO the first electrode.Prepare thereon identically with comparative example 1 insulating barrier with
Insulated column layer so that pixel size is 0.28mm × 0.28mm.After put into evaporation chamber in be deposited with hole transmission layer, luminescence successively
Layer, electron transfer layer, electron injecting layer, the second electrode lay.During evaporation, chamber pressure is less than 5.0 × 10-3Pa, is first deposited with
40nm thickness NPB is as hole transmission layer；ADN and TBPe thick for method evaporation 30nm steamed altogether using double source, as luminescent layer, passes through
Rate controlled TBPe ratio in ADN is 7%；The Alq of evaporation 20nm3As electron transfer layer；The Li conduct of evaporation 0.5nm
Electron injecting layer, the rear ITO using sputtering method to make 150nm is as the second electrode lay.
Table 1
Note: comparative example 3, embodiment 18, the luminosity that transparent devices brightness is device substrate face of embodiment 19.
By data above it can be seen that by the low-refraction grid layer adding the present invention, device brightness ratio is without grid layer
Device be significantly improved, the light showing the use of low-refraction grid layer really to add originally to be limited in device defeated
Go out.The brightness of the OLED that the OLED that wherein grid layer is placed on substrate is placed on the first electrode layer than grid layer is higher.And grid
When compartment refractive index is relatively low, device brightness is higher, shows to use the grid of more low-refraction, can make more to be limited in device
Interior light is output in arrival air.It addition, above example also illustrates that d1 and d2 of comb mesh pattern to the brightness of device also
There is significantly impact.
Claims (11)
1. an organic electroluminescence device, the following layers including stacking gradually: substrate, the first electrode layer, organic function layer,
Two electrode layers, and, it also includes one layer of low-refraction grid layer, and the refractive index of described grid layer is for more than 1.0 and less than institute
State the refractive index of organic function layer, described grid layer between substrate and the first electrode layer,
And in each pixel region, the pattern that the bossing of described grid layer is constituted is: a series of with concentric form
Layer by layer nested shape is identical and multiple n-shapeds that size is different or circle, wherein within the border of each pixel region,
Region area beyond maximum n-shaped or circle is more than 0 and not higher than 1/4 with the ratio of this pixel region gross area；Wherein N >=
3；In the pattern that the bossing of described grid layer is constituted, the width d1 of each maximum n-shaped or circular interior each bossing is
0.05 μm～20 μm, each maximum n-shaped or circular interior each space do not include the width d2 in the space in bosom
It is 1 μm～30 μm.
Organic electroluminescence device the most according to claim 1, it is characterised in that the refractive index of described grid layer is 1.0-
1.5。
Organic electroluminescence device the most according to claim 1, it is characterised in that the light transmittance of described grid layer is
75%-99%.
Organic electroluminescence device the most according to claim 1, it is characterised in that the thickness of described grid layer is 0.1 μm
～20 μm.
Organic electroluminescence device the most according to claim 1, it is characterised in that the thickness of described grid layer is 0.1 μm
～5 μm.
Organic electroluminescence device the most according to claim 1, it is characterised in that described n-shaped is equilateral triangle, just
Square or regular hexagon.
Organic electroluminescence device the most according to claim 1, it is characterised in that each maximum n-shaped or circular interior
Described bosom space width less than maximum n-shaped or circular in two times of other each gap length d2.
Organic electroluminescence device the most according to claim 7, it is characterised in that d1 is 0.05 μm to 5 μm, d2 is 1 μm
To 10 μm.
Organic electroluminescence device the most according to claim 8, it is characterised in that d1 is that 0.05 μm is to 3 μm.
Organic electroluminescence device the most according to claim 1, it is characterised in that described device uses transparent first
Electrode layer and the second electrode lay possessing reflection function, or use the first electrode layer and the transparent second electricity possessing reflection function
Pole layer, or use the first transparent electrode layer and transparent the second electrode lay.
11. 1 kinds of methods preparing organic light emitting display, its feature is included on substrate formation refractive index more than 1.0 and low
In the low-refraction grid layer of the refractive index of organic function layer, and low-refraction grid layer is made following pattern: its lobe
Point pattern constituted be a series of with concentric form layer by layer nested shape is identical and multiple n-shapeds that size is different or circle
Shape, wherein the region area within the border of each pixel region, beyond maximum n-shaped or circle is total with this pixel region
Area ratio is more than 0 and not higher than 1/4, wherein N >=3, each maximum n-shaped or circle in the pattern that described bossing is constituted
In shape, the width d1 of each bossing is 0.05 μm～20 μm, and each maximum n-shaped or circular interior each space do not include
The width d2 in the space in bosom is 1 μm～30 μm；Then the first electrode layer, the organic functions being laminated to each other it is sequentially depositing
Layer and the second electrode lay；Then encapsulate.
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| CN103972262B (en) * | 2013-11-19 | 2017-06-06 | 厦门天马微电子有限公司 | A kind of organic light-emitting display device and its manufacture method |
| CN103928625B (en) * | 2014-04-08 | 2016-05-18 | 陕西科技大学 | The device architecture of a kind of flexible and transparent OLED and preparation method |
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| CN101647134A (en) * | 2007-03-30 | 2010-02-10 | 密执安州立大学董事会 | OLED with improved light outcoupling |
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