CN103996797A - Organic light emitting device and manufacturing method thereof - Google Patents
Organic light emitting device and manufacturing method thereof Download PDFInfo
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- CN103996797A CN103996797A CN201410257397.2A CN201410257397A CN103996797A CN 103996797 A CN103996797 A CN 103996797A CN 201410257397 A CN201410257397 A CN 201410257397A CN 103996797 A CN103996797 A CN 103996797A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/854—Arrangements for extracting light from the devices comprising scattering means
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- H—ELECTRICITY
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Abstract
The invention discloses an organic light emitting device which is provided with a transparent substrate, a first electrode, an organic function layer, a second electrode and an optical coupling film layer. The first electrode, the organic function layer and the second electrode are arranged on one face of the transparent substrate and sequentially stacked, and the optical coupling film layer is arranged on the other face of the transparent substrate. The optical coupling film layer is provided with a layer body and a patterned layer arranged on the surface of the layer body; or the optical coupling film layer is provided with a layer body and micro holes distributed in the layer body or distributed in the surface of the layer body; or the optical coupling film layer is provided with a layer body, micro holes distributed in the layer body or distributed in the surface of the layer body, and a patterned layer arranged on the surface of the layer body. A manufacturing method of the organic light emitting device comprises the steps of (a) manufacturing the first electrode, the organic function layer and the second electrode on one face of the substrate in sequence, and (b) manufacturing the optical coupling film layer on the other face of the substrate. The organic light emitting device has the advantages of being easy to process, and good in light taking-out effect.
Description
Technical field
The present invention relates to organic semiconductor technical field, relate in particular to a kind of organic electroluminescence device that improves light extraction efficiency and preparation method thereof.
Background technology
The English full name of OLED(is Organic Light Emitting Diodes, the meaning is organic electroluminescence device, be called for short OLED) have that active illuminating, visual angle are wide, lightweight, temperature wide accommodation, area solidify greatly, complete, flexibility, the many merits such as low in energy consumption, fast response time and low cost of manufacture, showing with lighting field have important application, more and more receive the concern of academia and industrial quarters.
In prior art, generally select clear glass as the substrate of OLED device, the refractive index of glass is generally 1.55 left and right, and the refractive index of electroluminescent organic material layer is generally 1.7 left and right, and the refractive index of ITO layer is generally 1.8 left and right.The light sending after electroluminescent organic material energising, when process ITO layer enters glass, process glass enters air again, while being propagated to optically thinner medium by optically denser medium, can there is total reflection phenomenon, cause most of light to be confined in OLED device, cause the light output efficiency of OLED greatly to reduce, wherein approximately 40% light can be because the loss of ITO/ organic layer waveguide mode, approximately 10% light can be lost by SP pattern (surface plasma), 30% light can be confined to lose in (substrate) pattern, and 20% the luminous energy of only having an appointment is propagated out from glass substrate outside.Therefore, about 80% light is limited to or loss cannot rationally be applied in the inside of OLED electroluminescent organic material.
The method that raising oled light takes out at present has a variety of, and the people such as Kanchan Saxena are at document Optical Materials
32, the measure that multiple raising oled light takes out efficiency has been summarized in 221 (2009) the insides.By comparative study, find, the structure of outer surface is carried out to design improvement and to reach raising light taking-up effect, seem particularly simply and operability.The outer surface structure of substrate is processed and is promoted light taking-up efficiency, mainly contain following several mode:
The thin layer of scattering layer, chemical method formation porous etc. is pasted, is coated with to roughening substrate surface, formation microlens array, individual layer and multilayer optical coupling film, formation light extraction film.
But still there is many defects in these exterior light technology of taking out at present:
1) roughening substrate surface mainly contains blasting craft and two kinds of methods of chemical corrosion.Blasting craft, with specific angle and speed, to be ejected into glass substrate surface with the granule that the sand-blasting machine customizing is micron level by diameter, high velocity particle brings corresponding mechanical oscillation inevitably to whole device to the impact meeting of substrate outer surface, upset well arranging between molecule in oled layer, to the optical property of device and electric property, all can make a big impact, thereby affect OLED life-span and stability.While using chemicals directly etching glass surface, the product of same batch may have diverse outer surface pattern, makes the poor consistency of device, is unfavorable for commercially producing.No matter use blasting craft or chemical corrosion, all can have image blurring phenomenon in various degree.
2) while improving light taking-up efficiency as use lenticule, lenticule film needs the two-way array array of micron level, and this needs very accurate controlling dimension and stricter technique, causes complicated process of preparation, and cost is higher.In addition, if micro lens technology will be applied to demonstration field, need to dwindle and array lenticule, but now become quite important with the contraposition of substrate, and substrate can not too thick (< 0.5mm), otherwise neighbor can interfere with each other, and image shows fuzzy.In any case, while using micro lens technology to promote light taking-up effect, always have image blurring phenomenon in various degree.
3), while using individual layer optical coupling film, the basic manufacture method of the method is at the specific material of OLED outside deposition, such as MgF
2although its refractive index is 1.38 (wavelength 550 nm), between air and glass, its refractive index changes with wavelength is different, and for monochromatic light, the light of each wavelength period takes out required MgF
2thickness is different, need to carry out accuracy controlling, and this kind of mode be obviously unfavorable for that the light of white light takes out effect, and the taking-up effect of the method is also relatively poor.Process costs is higher to use multilayer optical coupling layer, and material selection scope is also less simultaneously.
4) adopting light to extract film pastes, it is poor that light takes out effect, owing to needing the tack coat of index matching, and the light transmission of tack coat also had to requirement, cause this tack coat selection range less, the light extraction efficiency that existing this method obtains generally only has 20% ~ 30% to promote.
5) coating scattering layer is the method that effective light extracts, the method processing is simple, it is more excellent that light takes out effect, but scattering particles, dispersant, solvent to be ground to the rear leaching filtrate of crossing owing to relating to, again gained filtrate is mixed with matrix and made scattering layer solution, and make technique relative complex, and also between inevitable scattering particles, can produce agglomeration, thereby affect light, take out effect.
(6) chemical method obtains the film of porous, and technological parameter is adjusted complicated, also needs to use expensive equipment in technique.
Visible, there is the features such as impact or complicated process of preparation to other performances of device in processing method ubiquity of the prior art.Therefore, not enough for prior art, provide a kind of light take out effective, preparation technology simple and do not affect organic electroluminescence device of other performance of device and preparation method thereof, very necessary to overcome prior art deficiency.
Summary of the invention
The object of this invention is to provide and a kind ofly can improve organic electroluminescence device of light extraction efficiency and preparation method thereof, there is light and take out feature effective and that processing mode is simple, device performance is good.
Above-mentioned purpose of the present invention realizes by following technological means:
An organic electroluminescence device, is provided with transparent substrates, is arranged at transparent substrates one side and folds successively the first electrode, organic function layer and the second electrode of establishing and the optical coupling thin layer that is arranged at described transparent substrates another side;
The patterned layer that described optical coupling thin layer is provided with layer body and is arranged at layer surface; Or
The micropore that described optical coupling thin layer is provided with layer body and is distributed in layer body inside or layer surface; Or
Described optical coupling thin layer is provided with a layer body, is distributed in layer body inside or the micropore of layer surface and the patterned layer that is arranged at layer surface.
Above-mentioned optical coupling thin layer visible light transmissivity is greater than 60%, and refractive index is greater than 1.6, and described optical coupling thin layer thickness is 1 ~ 1000 micron.
Above-mentioned layer body is hyaline layer body, the material of layer body can be polymethyl methacrylate (PMMA), polyimides (PI), dimethyl silicone polymer (PDMS), polyethylene terephthalate (PET), epoxy resin (EP), Merlon (PC), nylon (PA), acrylonitrile one styrol copolymer (AS), transparent polypropylene (PP), transparent ABS (acrylonitrile-butadiene-styrene copolymer), BS polychlorostyrene (BS), ethene (PVC), PEN (PEN), at least one in polyethersulfone resin (PES) or polymine (PEI).
Preferably, above-mentioned patterned layer is set to regular microlens array or is set to irregular relief pattern, and the duty ratio of described patterned layer is greater than 0.1.
Further, above-mentioned patterned layer is set to intensive pattern type film, and the duty ratio of described patterned layer is 0.25-0.5, and the maximum gauge scope of each monomer is 1-500 micron.
Another is preferred, above-mentioned micropore maximum gauge be 1-200 micron, the duty ratio of described layer body inside or surface micropore is greater than 0.1.
Further, above-mentioned optical coupling thin layer is set to dense micropore type film, and the duty ratio of described optical coupling thin layer inside or surface micropore is 0.25-0.5, and the maximum gauge scope of each micropore is 5-20 micron.
Above-mentioned optical coupling thin layer and described substrate are set to integrated formed structure, and described substrate is glass, polyesters compound or polyimides compounds.
A preparation method for organic electroluminescence device, is characterized in that: contain
A prepares the first electrode, organic function layer and the second electrode successively in the one side of substrate; With
B prepares optical coupling thin layer at substrate another side;
The patterned layer that described optical coupling thin layer is provided with layer body and is arranged at layer surface; Or
The micropore that described optical coupling thin layer is provided with layer body and is distributed in layer body inside or layer surface; Or
Described optical coupling thin layer is provided with a layer body, is distributed in layer body inside or the micropore of layer surface and the patterned layer that is arranged at layer surface.
Preferably, at substrate another side, preparing optical coupling thin layer specifically prepares by following technique:
First the transparent polymer having dissolved is in advance passed through to solution processing mode film forming on substrate another side; By heating or ultraviolet lighting, film precuring is formed to layer body again, utilize patterning is good seal, roller, by impression or letterpress mode, to Thinfilm pattern, form patterned layer, further by heating or ultraviolet lighting, make film hardening afterwards; Or
First the transparent polymer having dissolved is in advance passed through to solution processing mode film forming on substrate another side; Then disposable bone dry film, forms smooth film surface, then by the mode patterning of hot transfer printing.
Preferably, the optical coupling film that has a micropore in substrate another side preparation is to be in film forming procedure, to form micropore or form by outer needles sharp shaped material impression in the film forming later stage;
When forming micropore in film forming procedure, specifically in film forming process, process, by bubbling form micropore or
In film forming process, add extract and make solution differential loose, after then carrying out sheet, use solvent extraction extract, formation micropore or
In film forming process, add the solid matter of low melting point and make Solution Dispersion, after then carrying out sheet, by mode of heating, making solid granulates melting distillation, forming micropore;
When the film forming later stage forms by outer needles sharp shaped material impression, specifically, by solution processing mode film forming carrying out after precuring on substrate another side, by outside spicule impression, be processed to form pin hole, afterwards cured film completely.
Preferably at substrate another side, prepare in the preparation process of optical coupling thin layer, underlayer temperature is less than 80 ℃.
Organic electroluminescence device of the present invention and preparation method thereof, by simultaneously forming organic electroluminescence cell at substrate, forms optical coupling thin layer at substrate another side.The light that OLED produces, through transparent substrates after, then passes through optical coupling thin layer, has reduced light directly from extremely airborne total reflection of substrate transport, is conducive to the output of light.Meanwhile, preparation technology is simple for this optical coupling thin layer, is easy to large area film forming, and preparation cost is low, and process repeatability and operability are more excellent, are applicable to commercially producing.In addition, this optical coupling thin layer is the back side that acts on substrate, is arranged at respectively the both sides of glass substrate with OLED device, and both are not subject to impact each other mutually in preparation process.The preparation process of light optical coupling thin layer does not exert an influence to OLED electrology characteristics such as the voltage of OLED device, current density, spectrum.Therefore the present invention has light and takes out feature effective and that processing mode is simple, device performance is good.
Accompanying drawing explanation
The present invention is further illustrated to utilize accompanying drawing, but content in accompanying drawing does not form any limitation of the invention.
Fig. 1 is the structural representation of a kind of organic electroluminescence device of the present invention.
Fig. 2 is the spectrogram of device device under 4V voltage of the embodiment of the present invention 7;
Fig. 3 is the normalization spectrogram of device device under 4V voltage of the embodiment of the present invention 7;
Fig. 4 is the spectrogram of device device under 4V voltage of the embodiment of the present invention 8;
Fig. 5 is the normalization spectrogram of device device under 4V voltage of the embodiment of the present invention 8;
Fig. 6 is the structural representation of the substrate another side of the embodiment of the present invention 9 device A3;
Fig. 7 is the structural representation of the substrate another side of the embodiment of the present invention 9 device B3;
Fig. 8 is the structural representation of the substrate another side of the embodiment of the present invention 11 device B5.
Embodiment
The invention will be further described with the following Examples.
embodiment 1.
An organic electroluminescence device, as shown in Figure 1, is provided with transparent substrates, is arranged at transparent substrates one side and folds successively the first electrode, organic function layer and the second electrode of establishing and the optical coupling thin layer that is arranged at described transparent substrates another side.
The patterned layer that optical coupling thin layer is provided with layer body and is arranged at layer surface.Optical coupling thin layer visible light transmissivity is greater than 60%, and refractive index is greater than 1.6, and optical coupling thin layer thickness is 1 ~ 1000 micron.
The layer body of optical coupling thin layer is hyaline layer body, it is prepared material and can be polymethyl methacrylate (PMMA), polyimides (PI), dimethyl silicone polymer (PDMS), polyethylene terephthalate (PET), epoxy resin (EP), Merlon (PC), nylon (PA), acrylonitrile one styrol copolymer (AS), transparent polypropylene (PP), transparent ABS (acrylonitrile-butadiene-styrene copolymer), BS polychlorostyrene (BS), ethene (PVC), PEN (PEN), at least one in polyethersulfone resin (PES) or polymine (PEI).
The patterned layer of optical coupling thin layer is set to regular microlens array or is set to irregular relief pattern, and the duty ratio of patterned layer is greater than 0.1.Duty ratio refers to the area of projection and the ratio of entire area.Patterned layer is preferably set to intensive pattern type film, the duty ratio of intensive pattern type film is greater than 0.25, and the maximum gauge scope of each monomer is 1-500 micron, because the pattern of film is not necessarily regular, therefore with maximum gauge, describe, maximum gauge herein refers to the distance between farthest 2 of monomer distance.Research finds, when the duty ratio of patterned layer is 0.25-0.5, in particular for 0.5 o'clock, performance was best.
The technique that simultaneously forms organic electroluminescence cell at substrate is general knowledge known in this field, does not repeat them here.Patterned layer can be prepared from by following technique, and the transparent polymer having dissolved is in advance passed through to solution processing mode film forming on substrate another side; By heating or ultraviolet lighting, film precuring is formed to layer body again, utilize patterning is good seal, roller, by impression or letterpress mode, to Thinfilm pattern, form patterned layer, further by heating or ultraviolet lighting, make film hardening afterwards; Or first the transparent polymer having dissolved is in advance passed through to solution processing mode film forming on substrate another side; Then disposable bone dry film, forms smooth film surface, then by the mode patterning of hot transfer printing.
Optical coupling thin layer and substrate-like are integral molding structure, and substrate is glass, polyesters compound or polyimides compounds.
This organic electroluminescence device, by simultaneously forming organic electroluminescence cell at substrate, forms optical coupling thin layer at substrate another side.The light that OLED produces, through transparent substrates after, then passes through optical coupling thin layer, has reduced light directly from extremely airborne total reflection of substrate transport, is conducive to the output of light.Meanwhile, preparation technology is simple for this optical coupling thin layer, is easy to large area film forming, and preparation cost is low, and process repeatability and operability are more excellent, are applicable to commercially producing.In addition, this optical coupling thin layer is the back side that acts on substrate, is arranged at respectively the both sides of glass substrate with OLED device, and both are not subject to impact each other mutually in preparation process.The preparation process of light optical coupling thin layer does not exert an influence to OLED electrology characteristics such as the voltage of OLED device, current density, spectrum.There is light and take out feature effective and that processing mode is simple, device performance is good.
embodiment 2.
An organic electroluminescence device, further feature is identical with embodiment 1, and difference is: the micropore that optical coupling thin layer is provided with layer body and is distributed in layer body inside or layer surface.
The maximum gauge scope of micropore is 1-200 micron, and the duty ratio of layer surface micropore is greater than 0.1, and duty ratio refers to the ratio of layer area of surface micropore and layer bulk area.Because micropore should not be decided to be regular circular hole, therefore, the maximum gauge of micropore refers to the distance between farthest 2 of micropore herein.
Micropore can comprise any one or two kinds in perforate and closed pore framework.Micropore can have any applicable shape or size, as spherical, columniform, slot-shaped etc.If micropore is perforate, these micropores can form a plurality of passages or connect the path between micropore.This microcellular structure can have the volume of any applicable porosity, density or perforate and/or closed pore.In addition, micropore can carry out directional profile by any applicable structure shape, as random, orderly etc.
The technique that simultaneously forms organic electroluminescence cell at substrate is general knowledge known in this field, does not repeat them here.Micropore can form or form by outer needles sharp shaped material impression in the film forming later stage in film forming procedure.
When forming micropore in film forming procedure, specifically in film forming process, process, by bubbling mode, prepare micropore or by adding extract and making solution differential loose, after carrying out sheet, with extraction extracts such as solvents, form micropore or in film forming process, add the solid matter of low melting point and make Solution Dispersion, after then carrying out sheet, passing through mode of heating, make solid granulates melting distillation, form micropore.
When the film forming later stage forms by outer needles sharp shaped material impression, specifically, by solution processing mode film forming carrying out after precuring on substrate another side, by outside spicule impression, be processed to form pin hole, afterwards cured film completely.
This organic electroluminescence device, by simultaneously forming organic electroluminescence cell at substrate, forms the optical coupling thin layer with micropore at substrate another side.The light that OLED produces, through transparent substrates after, then passes through optical coupling thin layer, has reduced light directly from extremely airborne total reflection of substrate transport, is conducive to the output of light.Meanwhile, preparation technology is simple for this optical coupling thin layer, is easy to large area film forming, and preparation cost is low, and process repeatability and operability are more excellent, are applicable to commercially producing.In addition, this optical coupling thin layer is the back side that acts on substrate, is arranged at respectively the both sides of glass substrate with OLED device, and both are not subject to impact each other mutually in preparation process.The preparation process of light optical coupling thin layer does not exert an influence to OLED electrology characteristics such as the voltage of OLED device, current density, spectrum.There is light and take out feature effective and that processing mode is simple, device performance is good.
embodiment 3.
An organic electroluminescence device, further feature is identical with embodiment 1, and difference is: optical coupling thin layer is provided with a layer body, is distributed in layer body inside or the micropore of layer surface and the patterned layer that is arranged at layer surface.During preparation optical coupling thin layer, first prepare microcellular structure, afterwards at layer surface reprocessing patterned layer.There is light and take out feature effective and that processing mode is simple, device performance is good.
embodiment 4.
A preparation method for organic electroluminescence device, contains:
A prepares the first electrode, organic function layer and the second electrode successively in the one side of substrate; With
B prepares optical coupling thin layer at substrate another side; The patterned layer that optical coupling thin layer is provided with layer body and is arranged at layer surface.
Wherein the order of a and b can freely convert, and can also can first carry out b by advanced row a, or can operate simultaneously.
The technique of preparing successively the first electrode, organic function layer and the second electrode in the one side of substrate is general knowledge known in this field, does not repeat them here.
At substrate another side, preparing optical coupling thin layer specifically prepares by following technique:
First the transparent polymer having dissolved is in advance passed through to solution processing mode film forming on substrate another side; By heating or ultraviolet lighting, film precuring is formed to layer body again, utilize patterning is good seal, roller, by impression or letterpress mode, to Thinfilm pattern, form patterned layer, further by heating or ultraviolet lighting, make film hardening afterwards; Or
First the transparent polymer having dissolved is in advance passed through to solution processing mode film forming on substrate another side; Then disposable bone dry film, forms smooth film surface, then by the mode patterning of hot transfer printing.
Method of the present invention, by simultaneously forming organic electroluminescence cell at substrate, forms optical coupling thin layer at substrate another side.The light that OLED produces, through transparent substrates after, then passes through optical coupling thin layer, has reduced light directly from extremely airborne total reflection of substrate transport, is conducive to the output of light.Meanwhile, preparation technology is simple for this optical coupling thin layer, is easy to large area film forming, and preparation cost is low, and process repeatability and operability are more excellent, are applicable to commercially producing.In addition, this optical coupling thin layer is the back side that acts on substrate, is arranged at respectively the both sides of glass substrate with OLED device, and both are not subject to impact each other mutually in preparation process.The preparation process of light optical coupling thin layer does not exert an influence to OLED electrology characteristics such as the voltage of OLED device, current density, spectrum.There is light and take out feature effective and that processing mode is simple, device performance is good.
embodiment 5.
A preparation method for organic electroluminescence device, contains:
A prepares the first electrode, organic function layer and the second electrode successively in the one side of substrate; With
B prepares optical coupling thin layer at substrate another side; The micropore that optical coupling thin layer is provided with layer body and is distributed in layer body inside or layer surface.
Wherein the order of a and b can freely convert, and can also can first carry out b by advanced row a, or can operate simultaneously.
The optical coupling film in the preparation of substrate another side with micropore is to be in film forming procedure, to form micropore or by outer needles sharp shaped material, impress formation in the film forming later stage.It should be noted that, in the preparation process of preparation optical coupling thin layer, underlayer temperature is less than 80 ℃.
When forming micropore in film forming procedure, specifically in film forming process, process, by bubbling mode, form micropore or by adding extract and making solution differential loose, after carrying out sheet, with extraction extracts such as solvents, form micropore.
Capillary processing method is specially:
Can become viscosity to be greater than 15 pa.s solution transparent removing layer material formulation, by stirring, the modes such as bubbling, make to comprise a large amount of bubbles in solution, by modes such as blade coatings, are carrying out film forming afterwards, the dry rear film with micropore that forms.
Can also form microporous membrane by extracting process, being about to two or more removing layer materials is dissolved in another solvent, film forming on substrate, dry, with another solvent, extract afterwards, this solvent only dissolves a kind of in removing layer material or certain is several, but has at least a kind of material not dissolve.By this mode, be prepared into the film with micropore.
Also the material formulation of transparent removing layer can be become after certain density solution, the solid granulates that is insoluble to removing layer solvent that the inside is added some low melting points again as paraffin, hypo, how etc., size Control is at micron order, by modes such as blade coatings, carry out film forming again, under lower than these solid granulates melting ranges by removing layer material dry solidification, afterwards under higher than solid granulates melting temperature, further annealing in process, by solid granulates melting distillation.Or other solid-state foreign substances, to be dried after, adopt chemical corrosion mode to remove solid-state foreign substances.Obtain having the film of micropore.
When the film forming later stage forms by outer needles sharp shaped material impression, specifically, by solution processing mode film forming carrying out after precuring on substrate another side, by outside spicule impression, be processed to form pin hole, afterwards cured film completely.
Pin hole processing method is specifically:
Choose the thin draw point in required aperture, according to the pitch-row row of will hoping for success, arrange, afterwards according to particular row apart from requiring to sting out the aperture that rule is arranged; Also can, directly with the thin draw point in required aperture, prepare disorderly and unsystematic aperture of arranging.If transparent removing layer refractive index is less than selected OLED refractive index of substrate, it is removing layer thickness that draw point thrusts the degree of depth, need thrust to substrate place, but can not damage substrate.If transparent removing layer refractive index is greater than selected OLED refractive index of substrate, draw point thrusts the degree of depth and is greater than 0 but be less than removing layer thickness.
Method of the present invention, by simultaneously forming organic electroluminescence cell at substrate, forms optical coupling thin layer at substrate another side.The light that OLED produces, through transparent substrates after, then passes through optical coupling thin layer, has reduced light directly from extremely airborne total reflection of substrate transport, is conducive to the output of light.Meanwhile, preparation technology is simple for this optical coupling thin layer, is easy to large area film forming, and preparation cost is low, and process repeatability and operability are more excellent, are applicable to commercially producing.In addition, this optical coupling thin layer is the back side that acts on substrate, is arranged at respectively the both sides of glass substrate with OLED device, and both are not subject to impact each other mutually in preparation process.The preparation process of light optical coupling thin layer does not exert an influence to OLED electrology characteristics such as the voltage of OLED device, current density, spectrum.There is light and take out feature effective and that processing mode is simple, device performance is good.
embodiment 6.
A preparation method for organic electroluminescence device, contains:
A prepares the first electrode, organic function layer and the second electrode successively in the one side of substrate; With
B prepares optical coupling thin layer at substrate another side.
Optical coupling thin layer is provided with a layer body, is distributed in layer body inside or the micropore of layer surface and the patterned layer that is arranged at layer surface.Its preparation process is first to prepare the layer body with microcellular structure, then in layer surface, prepares patterned layer.
Method of the present invention, by simultaneously forming organic electroluminescence cell at substrate, forms optical coupling thin layer at substrate another side.The light that OLED produces, through transparent substrates after, then passes through optical coupling thin layer, has reduced light directly from extremely airborne total reflection of substrate transport, is conducive to the output of light.Meanwhile, preparation technology is simple for this optical coupling thin layer, is easy to large area film forming, and preparation cost is low, and process repeatability and operability are more excellent, are applicable to commercially producing.In addition, this optical coupling thin layer is the back side that acts on substrate, is arranged at respectively the both sides of glass substrate with OLED device, and both are not subject to impact each other mutually in preparation process.The preparation process of light optical coupling thin layer does not exert an influence to OLED electrology characteristics such as the voltage of OLED device, current density, spectrum.There is light and take out feature effective and that processing mode is simple, device performance is good.
embodiment 7.
Below in conjunction with detailed experimental example, further the present invention will be described.
First used material is described:
ITO: tin indium oxide;
SU-8: transparent photomask glue;
NPB:(N, N'-diphenyl-N, N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines);
C545T:2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9,9A, 1GH] cumarin;
Alq
3: 8-hydroxyquinoline aluminum;
LiF: lithium fluoride;
Al: aluminium.
Adopt the method preparation of embodiment 4, with B(x) (functional layer title) represent the one deck in structure, and it makes material is B, and the thickness of this layer is x (dust).
The structure of prepared device B1 is: SU-8 patterned film/Glass(substrate)/ITO(anode)/NPB (200) (hole transmission layer)/Alq3:C545T(green fluorescence luminescent layer) (300)/Alq
3(electron transfer layer) (300)/LiF (10) (electron injecting layer)/Al (2000) (negative electrode).
For the ease of comparison, with above-mentioned identical method, prepare comparative device A1, the structure of device A1 is:
Glass(substrate)/ITO(anode)/NPB (200) (hole transmission layer)/Alq3:C545T(green fluorescence luminescent layer) (300)/Alq
3(electron transfer layer) (300)/LiF (10) (electron injecting layer)/Al (2000) (negative electrode).
It is substrate that device A1, B1 all adopt glass, refractive index=1.55, and wherein device A1 is the device that there is no Light outcoupling layer, the Light outcoupling layer of device B1 is SU-8 film (refractive index=1.5).From Fig. 3, can significantly find out,, without the device A1 of Light outcoupling layer, the light intensity of device B1 effectively improves.From the normalization spectrum of Fig. 4, can find out, the optical characteristics of device changes hardly, and the chromaticity coordinates of device changes hardly, and under this voltage (4 V), the brightness of device A1 is 171 cd/m
2, the brightness of device B1 is 225 cd/m
2, light takes out effect and effectively promotes 31.6%.
Visible, the present invention has light and takes out feature effective and that processing mode is simple, device performance is good.
embodiment 8.
Below in conjunction with detailed experimental example, further the present invention will be described.
First used material is described:
PDMS: dimethyl silicone polymer;
ITO: tin indium oxide;
NPB:(N, N'-diphenyl-N, N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamines);
BH-428: blue light main body, purchased from Taiwan Yu Lei Optoelectronics Technology company;
EB613: blue light object, purchased from Taiwan Yu Lei Optoelectronics Technology company;
Alq
3:8-hydroxyquinoline aluminum;
C545T:2,3,6,7-tetrahydrochysene-1,1,7,7-tetramethyl-1H, 5H, 11H-10-(2-[4-morpholinodithio base)-quinolizino [9,9A, 1GH] cumarin;
LiF: lithium fluoride;
Al: aluminium.
Adopt the method preparation of embodiment 4, the structure of prepared device B2 is: PDMS patterned film/Glass(substrate)/ITO(anode)/NPB (200) (hole transmission layer)/BH-428:EB613(blue luminescence layer) (300)/Alq
3(electron transfer layer) (300)/LiF (10) (electron injecting layer)/Al (2000) (negative electrode).
For the ease of comparison, with identical method, prepare comparative device A2, the structure of device A2 is: Glass(substrate)/ITO(anode)/NPB (200) (hole transmission layer)/BH-428:EB613(blue luminescence layer) (300)/Alq
3(electron transfer layer) (300)/LiF (10) (electron injecting layer)/Al (2000) (negative electrode).
It is substrate that device A2, B2 all adopt glass, refractive index=1.55, and wherein device A2 is the device that there is no Light outcoupling layer, the Light outcoupling layer of device B2 is PDMS film (refractive index=1.5).From Fig. 4, can significantly find out,, without the device A2 of Light outcoupling layer, the light intensity of device B2 effectively improves.From the normalization spectrum of Fig. 5, can find out, the optical characteristics of device changes hardly, and the chromaticity coordinates of device changes hardly.And under this voltage (4 V), the brightness of device A2 is 101 cd/m
2, the brightness of device B2 is 143 cd/m
2, light takes out effect and effectively promotes 41.6%.
Visible, the present invention has light and takes out feature effective and that processing mode is simple, device performance is good.
embodiment 9.
Adopt the pin hole processing method of embodiment 5 to prepare device A3 and the device B3 with microcellular structure optical coupling thin layer.The optical coupling thin layer of device A3 is loose pore type film, as shown in Figure 6.The optical coupling thin layer of device B3 is dense micropore type film, as shown in Figure 7.Loose pore type film refers to that duty ratio is greater than 0.1 and be less than 0.25, and each micropore maximum gauge scope is the film of 40-60 micron.Dense micropore type film refers to that duty ratio is greater than 0.25, and each micropore maximum gauge scope is the film of 5-10 micron.
In the present embodiment, the duty ratio of the optical coupling thin layer of device A3 is 0.2, and the maximum gauge scope of micropore is 48-55 micron.The duty ratio of the optical coupling thin layer of device B3 is 0.5, and the maximum gauge scope of micropore is 5-10 micron.
The concrete structure of device A3 and device B3 is as follows:
Device A3:SU-8 pore type film/Glass(substrate that loosens)/ITO(anode)/NPB (200) (hole transmission layer)/Alq3:C545T(green fluorescence luminescent layer) (300)/Alq
3(electron transfer layer) (300)/LiF (10) (electron injecting layer)/Al (2000) (negative electrode).
Device B3:SU-8 dense micropore type film/Glass(substrate)/ITO(anode)/NPB (200) (hole transmission layer)/Alq3:C545T(green fluorescence luminescent layer) (300)/Alq
3(electron transfer layer) (300)/LiF (10) (electron injecting layer)/Al (2000) (negative electrode).
It is substrate that device A3, B3 adopt glass, the light of two kinds of multi-form devices is taken out to effect and contrast.By comparative study, find, the optical characteristics of device A3, B3 is about the same, and the chromaticity coordinates of device changes hardly.But under 4 V time, the brightness of device A3 is 201 cd/m under voltage
2, the brightness of device B3 is 243 cd/m
2.More unglazed removing layer device---brightness 171 cd/m of the device A1 in embodiment 7
2compare, the light of device A3 takes out effect and effectively promotes 17.5%, and the light of device B3 takes out effect and effectively promotes 42.1%.The light taking-up effect that dense micropore type structure devices is described is well more a lot of than evacuating pore type structure devices effect.
embodiment 10.
Adopt the impression mode of embodiment 4 to prepare the device B4 with patterning optical coupling thin layer, for the ease of contrast, adopt the device A4 that preparation in a like fashion does not have optical coupling thin layer.
The concrete structure of device A4 and device B4 is as follows:
Device A4:Glass(substrate)/ITO(anode)/NPB (200) (hole transmission layer)/Alq3:C545T(green fluorescence luminescent layer) (300)/Alq
3(electron transfer layer) (300)/LiF (10) (electron injecting layer)/Al (2000) (negative electrode).
Device B4:SU-8 is embossed into film patterning film/Glass(substrate)/ITO(anode)/NPB (200) (hole transmission layer)/Alq3:C545T(green fluorescence luminescent layer) (300)/Alq
3(electron transfer layer) (300)/LiF (10) (electron injecting layer)/Al (2000) (negative electrode).
It is substrate that device A4, B4 adopt glass, by comparative study, find, device A4,, the optical characteristics of B4 is about the same, the chromaticity coordinates of device changes hardly.But under identical voltage 4V, the brightness of device B4 is 262 cd/m
2, and the brightness of the device A4 of unglazed removing layer is 171 cd/m
2, the light of visible device B4 takes out effect and has effectively promoted 53.2%.
embodiment 11.
Adopt bubbling mode to form micropore, and adopt impression thin film-forming method to form picture on surface layer, be prepared into device B5, as shown in Fig. 8.
The concrete structure of device B5 and device A5 is as follows:
Device B5:SU-8 bubbling micropore and be embossed into film patterning film/Glass(substrate)/ITO(anode)/NPB (200) (hole transmission layer)/Alq3:C545T(green fluorescence luminescent layer) (300)/Alq3(electron transfer layer) (300)/LiF (10) (electron injecting layer)/Al (2000) (negative electrode).
Device A5:Glass(substrate)/ITO(anode)/NPB (200) (hole transmission layer)/Alq3:C545T(green fluorescence luminescent layer) (300)/Alq3(electron transfer layer) (300)/LiF (10) (electron injecting layer)/Al (2000) (negative electrode).
It is substrate that device A5, B5 adopt glass, by comparative study, finds, the optical characteristics of device A5, B5 is about the same, and the chromaticity coordinates of device changes hardly.But under identical voltage 4 V, the brightness of device B5 is 275 cd/m
2, compared with the brightness of device A5 171 cd/m
2, device B5 light takes out effect and effectively promotes 60.8%.Light extraction effect is good.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention; although the present invention is explained in detail with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify or be equal to replacement technical scheme of the present invention, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. an organic electroluminescence device, is characterized in that:
Be provided with transparent substrates, be arranged at transparent substrates one side and fold successively the first electrode, organic function layer and the second electrode of establishing and the optical coupling thin layer that is arranged at described transparent substrates another side;
The patterned layer that described optical coupling thin layer is provided with layer body and is arranged at layer surface; Or
The micropore that described optical coupling thin layer is provided with layer body and is distributed in layer body inside or layer surface; Or
Described optical coupling thin layer is provided with a layer body, is distributed in layer body inside or the micropore of layer surface and the patterned layer that is arranged at layer surface.
2. organic electroluminescence device according to claim 1, is characterized in that: described optical coupling thin layer visible light transmissivity is greater than 60%, and refractive index is greater than 1.6, and described optical coupling thin layer thickness is 1 ~ 1000 micron.
3. organic electroluminescence device according to claim 2, it is characterized in that: described layer body is hyaline layer body, and the material of described layer body is at least one in polymethyl methacrylate, polyimides, dimethyl silicone polymer, polyethylene terephthalate, epoxy resin, Merlon, nylon, acrylonitrile one styrol copolymer, transparent polypropylene, transparent propene nitrile-BS, BS polychlorostyrene, ethene, PEN, polyethersulfone resin or polymine.
4. according to the organic electroluminescence device described in claims 1 to 3 any one, it is characterized in that: described patterned layer is set to regular microlens array or is set to irregular relief pattern, and the duty ratio of described patterned layer is greater than 0.1.
5. organic electroluminescence device according to claim 4, is characterized in that: described patterned layer is set to intensive pattern type film, and the duty ratio of described patterned layer is 0.25-0.5, and the maximum gauge scope of each monomer is 1-500 micron.
6. according to the organic electroluminescence device described in claims 1 to 3 any one, it is characterized in that: the maximum gauge scope of described micropore is 1 ~ 200 micron, the duty ratio of described layer surface micropore is greater than 0.1.
7. organic electroluminescence device according to claim 6, it is characterized in that: described optical coupling thin layer is set to dense micropore type film, the duty ratio of described optical coupling thin layer surface micropore is 0.25-0.5, and each micropore maximum gauge scope is 5-20 micron.
8. the preparation method of the organic electroluminescence device as described in claim 1 to 6 any one, is characterized in that: contain
A prepares the first electrode, organic function layer and the second electrode successively in the one side of substrate; With
B prepares optical coupling thin layer at substrate another side;
The patterned layer that described optical coupling thin layer is provided with layer body and is arranged at layer surface; Or
The micropore that described optical coupling thin layer is provided with layer body and is distributed in layer body inside or layer surface; Or
Described optical coupling thin layer is provided with a layer body, is distributed in layer body inside or the micropore of layer surface and the patterned layer that is arranged at layer surface.
9. the preparation method of organic electroluminescence device according to claim 7, is characterized in that: at substrate another side, prepare optical coupling thin layer and specifically by following technique, prepare:
First the transparent polymer having dissolved is in advance passed through to solution processing mode film forming on substrate another side; By heating or ultraviolet lighting, film precuring is formed to layer body again, utilize patterning is good seal, roller, by impression or letterpress mode, to Thinfilm pattern, form patterned layer, further by heating or ultraviolet lighting, make film hardening afterwards; Or
First the transparent polymer having dissolved is in advance passed through to solution processing mode film forming on substrate another side; Then disposable bone dry film, forms smooth film surface, then by the mode patterning of hot transfer printing.
10. the preparation method of organic electroluminescence device according to claim 7, is characterized in that:
The optical coupling film in the preparation of substrate another side with micropore is to be in film forming procedure, to form micropore or by outer needles sharp shaped material, impress formation in the film forming later stage;
When forming micropore in film forming procedure, specifically in film forming process, process, by bubbling form micropore or
In film forming process, add extract and make solution differential loose, after then carrying out sheet, use solvent extraction extract, formation micropore or
In film forming process, add the solid matter of low melting point and make Solution Dispersion, after then carrying out sheet, by mode of heating, making solid granulates melting distillation, forming micropore;
When the film forming later stage forms by outer needles sharp shaped material impression, specifically, by solution processing mode film forming carrying out after precuring on substrate another side, by outside spicule impression, be processed to form pin hole, afterwards cured film completely.
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Application publication date: 20140820 |