CN107046047A - Pixel cell of printed form electroluminescent device and its preparation method and application - Google Patents

Pixel cell of printed form electroluminescent device and its preparation method and application Download PDF

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Publication number
CN107046047A
CN107046047A CN201610695573.XA CN201610695573A CN107046047A CN 107046047 A CN107046047 A CN 107046047A CN 201610695573 A CN201610695573 A CN 201610695573A CN 107046047 A CN107046047 A CN 107046047A
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China
Prior art keywords
electrode
layer
pixel
film layer
electroluminescent device
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Chinese (zh)
Inventor
李哲
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Guangdong Juhua Printing Display Technology Co Ltd
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Guangdong Juhua Printing Display Technology Co Ltd
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Priority to CN201610695573.XA priority Critical patent/CN107046047A/en
Publication of CN107046047A publication Critical patent/CN107046047A/en
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/33Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being semiconductor devices, e.g. diodes
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10OLED displays
    • H10K59/12Active-matrix OLED [AMOLED] displays
    • H10K59/121Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10OLED displays
    • H10K59/12Active-matrix OLED [AMOLED] displays
    • H10K59/121Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements
    • H10K59/1213Active-matrix OLED [AMOLED] displays characterised by the geometry or disposition of pixel elements the pixel elements being TFTs
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10OLED displays
    • H10K59/12Active-matrix OLED [AMOLED] displays
    • H10K59/122Pixel-defining structures or layers, e.g. banks
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass

Abstract

The present invention relates to a kind of pixel cell of printed form electroluminescent device and its preparation method and application, belong to illumination/technical field of display panel.The pixel cell includes:Substrate, first electrode, pixel defining layer, light emitting functional layer and second electrode, first electrode is located on substrate, pixel defining layer is formed on substrate and first electrode, and in position corresponding with first electrode provided with the pixel hole for accommodating marking ink, the pixel cell also includes transparent film layer, light emitting functional layer and second electrode are cascadingly set in the pixel hole, and cover first electrode, the base portion covering second electrode of film layer, top has raised radian, and the refractive index of film layer is more than air refraction and less than the refractive index of the second electrode.The pixel cell has the film layer structure of appropriate index and the shape that raises up, and the packaging protection of water oxygen is completely cut off to electroluminescent device formation to improve the life-span, while can also strengthen the light extraction efficiency of electroluminescent device.

Description

Pixel cell of printed form electroluminescent device and its preparation method and application
Technical field
The present invention relates to illumination/technical field of display panel, more particularly to a kind of picture of printed form electroluminescent device Plain unit and its preparation method and application.
Background technology
Printed form electroluminescent device must use one layer of material for being used to define pixel, the layer material in preparation process Commonly known as Bank.There are " container " of numerous sunk areas as ink, also referred to as picture in Bank layers (pixel defining layer) Element hole, each sunk area corresponds to a pixel.Technological process widely used at present, is to use InkJet printing processes by ink Water inserts each pixel region, first electrode (also referred to as pixel electrode) upper berth of ink in the region that pixel defining layer is surrounded Exhibition;Then, it is dried in vacuo under certain temperature (such as low temperature), by strictly controlling the rate of volatilization of solvent, solvent to steam The parameters such as vapour pressure are uniformly dried with ensureing to obtain between different zones, different pixels in pixel as far as possible;Finally, made by baking Film is thoroughly dried.After organic layer, second electrode prepare completion, finally electroluminescent device/panel is packaged.Have When, in order to improve the light extraction efficiency of electroluminescent device, in addition it is also necessary to increase necessary optical thin film, light extraction efficiency is improved, with The luminous energy for helping electroluminescent device to send preferably is extracted from device.
Also, in order to completely cut off the destruction of the water and oxygen in the external world to electroluminescent device, it will usually use film or cofferdam Wrapped up, encapsulated and protected.
The content of the invention
Based on this, the present invention provides a kind of pixel cell of printed form electroluminescent device and its preparation method and application, The structure of the pixel cell has the function of light extraction, and the effect passed through with exclusion of water and oxygen.
A kind of pixel cell of printed form electroluminescent device, including:Substrate, first electrode, pixel defining layer, luminous work( Ergosphere and second electrode, the first electrode are located on the substrate, and the pixel defining layer is formed at the substrate and described In first electrode, and in the position corresponding with the first electrode provided with the pixel hole for accommodating marking ink, in addition to film Layer, the light emitting functional layer and the second electrode are cascadingly set in the pixel hole, and cover the first electrode, The base portion of the film layer covers the second electrode, and the top of the film layer has raised radian, and the film layer It is made of clear material, the refractive index of the film layer is more than air refraction and less than the refractive index of the second electrode.
The present inventor has found that generally, pixel is defined after thoroughgoing and painstaking research is carried out to printed form electroluminescent device The thickness of layer is 1-1.5 μm, and the element is defined can accommodate after the ink of 50-200pL (picoliters), ink dried in the pixel hole of layer The membrane structure with lighting function, i.e. light emitting functional layer are formed, the thickness of such light emitting functional layer is typically in the range of 10- Between 150nm, therefore, the light emitting functional layer of whole electroluminescent device, the gross thickness of second electrode are generally between 200nm- Between 400nm.Estimate accordingly, electroluminescent device is completed after preparing, define the sky for also having 0.6-1.3 μm of depth in pixel region Between be not used by.
On the basis of the studies above, the proposition of the invention, by effectively utilizing the residue in pixel delimited area Space, forms the film layer transparent configuration with appropriate index and the shape that raises up, and electroluminescent device formation is completely cut off The packaging protection of water oxygen is to improve the life-span, while can also strengthen the light extraction efficiency of electroluminescent device.
Because:On the one hand, the transparent configuration with convex shape, the transparent knot of film layer of such as convex lens shape Structure, can be converged the light of diverging by refraction action in exit direction, so as to strengthen on display screen view direction Brightness;On the other hand, raised film layer transparent configuration can be by a part because total reflection or waveguide mode are trapped in device Light in part reflexes to the first electrode also with reflex of device opposite side, eventually through repeated reflection from device Inside is extracted, and the light extraction efficiency of electroluminescent device is improved on the whole.
Accordingly, a pixel cell corresponds to a pixel hole, and first electrode is directly exposed in the bottom in pixel hole, at this Light emitting functional layer, second electrode and film layer are sequentially provided with first electrode, the pixel cell of top emitting is constituted, except first electrode Outside, the light emitting functional layer, second electrode and film layer cheat madial wall (material for defining pixel) by pixel and limit its position Put.
In one of the embodiments, the inwall in the pixel hole is the slope that angle is 10 ° -70 °.Inwall is slope Pixel is cheated, and can make covering second electrode and its lower structure that film layer is more preferable, more closed, plays more preferably packaging protection work With.
In one of the embodiments, the contact between the transparent material of the film layer and the pixel defining layer material The scope of angle beta is 30 ° -90 °.Contact angle β between the film layer and the pixel defining layer can be utilized within this range Material property, obtains the film layer structure that preferable surface raises up, and the light for further increasing the electroluminescent device is carried Take efficiency.
In one of the embodiments, the film layer includes the multilayer knot that at least two different refractivity materials are made Structure, and often the refractive index of Rotating fields is gradually reduced on the direction away from substrate.For example, refractive index is gradually reduced by 1.5-2.0 To 1.0-1.5, such index distribution advantageously reduces total reflection of light when through top electrodes.
In one of the embodiments, the film layer maximum gauge is not less than 0.5 μm.It is preferred that 0.5-100 μm.Will be described The maximum gauge of film layer is set according to above-mentioned requirements, can effectively stop the transmission of water and oxygen.
In one of the embodiments, the film layer is made up of at least one of following material:Molecular weight is less than 2000 organic molecule, organic polymer resin, organosilicon, metal oxide, metal sulfide, Si oxide, silicon oxynitride, And silicon nitride.According to demand, the film layer can both prepare for a kind of material, or the mixture of multiple material.
In one of the embodiments, the film layer is made up of at least one of following material:Polyamide, polypropylene Cyanogen, polybutylene terephthalate (PBT), makrolon, polymethyl methacrylate, polyethylene, it is poly- to benzene diethyl sulfone, poly- pair Polyethylene terephthalate, PEN, polyimides, polypropylene, polystyrene, polysulfones, polyvinyl chloride, poly- silicon Oxygen alkane, polyvinylidene fluoride, polyvinyl acetate, polyureas, polytetrafluoroethylene (PTFE) and epoxy resin.Above-mentioned one kind can specifically be used Or several combinations, when using polymer monomer, it should polymerize monomer to form poly- with necessary heating or illumination methods Compound.
The bright preparation method for also disclosing above-mentioned pixel cell of this law, comprises the following steps:
Prepare first electrode:First electrode pattern is prepared on the substrate with TFT drive circuits;
Prepare pixel defining layer:Pixel defining layer is prepared on aforesaid substrate and first electrode, and is made by photoetching process The pixel defining layer forms corresponding pixel hole;
Prepare light emitting functional layer and second electrode:It is sequentially prepared out in above-mentioned pixel hole above first electrode described luminous Functional layer and the second electrode, the light emitting functional layer at least include one layer of luminescent layer;
Prepare film layer:In above-mentioned pixel hole the film layer is prepared above second electrode.
In one of the embodiments, in the preparation film layer step, using inkjet printing and/or the side of extrusion processing Formula forms the film layer;
The concrete mode of the inkjet printing is:The solution of film layer material is inserted into pixel hole in the way of inkjet printing It is interior, it is covered on second electrode, then solvent is volatilized, and removes residual solvent and moisture;
It is described extrusion processing concrete mode be:The film layer material extrusion for heating fusing is inserted in pixel hole, covering On second electrode, temperature is set to be slowly dropped to room temperature.
This law is bright to also disclose a kind of light-emitting display device, the pixel list with above-mentioned printed form electroluminescent device Member.
Aforementioned display device part is top emitting device, including organic electroluminescence device (OLED), quanta point electroluminescent device Part (QLED).
Compared with prior art, the invention has the advantages that:
The pixel cell of a kind of printed form electroluminescent device of the present invention, by effectively utilizing in pixel delimited area Space, forms the film layer transparent configuration with appropriate index and the shape that raises up, and electroluminescent device formation is completely cut off The packaging protection of water oxygen is to improve the life-span, while can also strengthen the light extraction efficiency of electroluminescent device.
Also, also pass through the sieve of the selection of the specific setting cheated to pixel, pixel defining layer material and film layer material etc. Choosing, further increases the packaging protection effect and light extraction efficiency of the film layer.
A kind of preparation method of pixel cell of the present invention, above-mentioned pixel list is prepared by practical, reliable way Member, it is possible to increase the light-emitting display device performance finally given.
A kind of light-emitting display device of the present invention, with above-mentioned pixel cell, therefore, it is possible to completely cut off the erosion of water oxygen, is carried The high life-span of electroluminescent device, and improve the light extraction efficiency and external quantum efficiency of electroluminescent device.
Brief description of the drawings
Fig. 1 is schematic diagram after preparation second electrode in embodiment;
Fig. 2 is pixel cell schematic diagram of the contact line at the top of pixel defining layer in embodiment;
Fig. 3 is single pixel cellular construction schematic diagram in Fig. 2;
Fig. 4 is pixel cell schematic diagram of the contact line in the middle part of pixel defining layer in embodiment.
Wherein:100. substrate;200. first electrode;300. pixel defining layer;310. pixels are cheated;400. light emitting functional layers and Second electrode (not separately labeled);500. film layer.
Embodiment
For the ease of understanding the present invention, the present invention is described more fully below with reference to relevant drawings.In accompanying drawing Give presently preferred embodiments of the present invention.But, the present invention can be realized in many different forms, however it is not limited to this paper institutes The embodiment of description.On the contrary, the purpose for providing these embodiments is to make the understanding to the disclosure more thorough Comprehensively.
Unless otherwise defined, all of technologies and scientific terms used here by the article is with belonging to technical field of the invention The implication that technical staff is generally understood that is identical.Term used in the description of the invention herein is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases The arbitrary and all combination of the Listed Items of pass.
A kind of pixel cell, including:Substrate, first electrode, pixel defining layer, light emitting functional layer, second electrode and film Layer, the first electrode is located on the substrate, and the pixel defining layer is formed on the substrate and the first electrode, and In the position corresponding with the first electrode provided with the pixel hole for accommodating marking ink, the light emitting functional layer and described second Electrode is cascadingly set in pixel hole, and covers the first electrode, the base portion covering of the film layer described the Two electrodes, the top of the film layer has raised radian, and the film layer is made of clear material, the film layer Refractive index is more than air refraction and less than the refractive index of the second electrode.
In some embodiments, first electrode can be anode, and second electrode can be negative electrode, flexible according to actual conditions Selection.Also, if necessary, light emitting functional layer also includes hole injection layer, hole transmission layer, electron injecting layer, electronics biography Defeated layer etc..
The present invention is by effectively utilizing the remaining space in pixel delimited area, and being formed has appropriate index and convex The film layer transparent configuration of shape is played, the packaging protection of water oxygen is completely cut off to electroluminescent device formation to improve the life-span, also simultaneously The light extraction efficiency of electroluminescent device can be strengthened, that is, form a kind of transparent configuration with " light extraction+encapsulation " dual-use function.
It should be understood that the transparent film layer is only needed with the structure raised up, such as convex lens shape, circular cone Shape, polygonal pyramid type, frustoconical, truncated pyramid etc., still, such as there is the round and smooth radian of convex lens shape, with preferable effect.
, can in different ways, when transparent material and the pixel of the film layer for how to prepare film layer The scope for defining contact angle β between layer material is 30 ° -90 °, can by the spreadability of material in itself directly, facilitate and must obtain The shape and structure that preferable surface raises up.
It again it will be understood that, it is contemplated that make covering second electrode and its lower structure that film layer is more preferable, more closed, play More preferably packaging protection is acted on, and the inwall that can cheat the pixel is set to the slope that angle is 10 ° -70 °.
For the refractive index of the film layer, it is only necessary to more than air refraction and less than second electrode refractive index, and can The single layer structure being made for a kind of material, or the sandwich construction that at least two materials are made, when the film layer includes During the sandwich construction that at least two different refractivity materials are made, per Rotating fields refractive index away from substrate direction on gradually Reduction, for example refractive index is gradually reduced to 1.0-1.5 scope by 1.5-2.0 scope, is advantageously reduced light and is being passed through top Total reflection during electrode..
It is described simultaneously in view of effectively stopping water and oxygen, and effective remaining space using in pixel delimited area Film layer maximum gauge is not less than 0.5 μm.The film layer maximum gauge refers under the base portion contacted from film layer with second electrode Distance of the surface to the summit of the upper surface of film layer top bump.
The material of the film layer, can be organic material or inorganic material, or multiple material mixing Thing, for example, can be made up of at least one of following material:Molecular weight less than 2000 organic molecule, organic polymer resin, Organosilicon, metal oxide, metal sulfide, Si oxide, silicon oxynitride and silicon nitride.According to demand, the film layer both may be used Think that a kind of material is prepared, or the mixture of multiple material.
It is preferred that, the film layer is made up of at least one of following material:It is polyamide, polypropylene cyanogen, poly- to benzene two It is formic acid butanediol ester, makrolon, polymethyl methacrylate, polyethylene, poly- to benzene diethyl sulfone, poly terephthalic acid second two Ester, PEN, polyimides, polypropylene, polystyrene, polysulfones, polyvinyl chloride, polysiloxanes, poly- inclined two PVF, polyvinyl acetate, polyureas, polytetrafluoroethylene (PTFE) and epoxy resin.Above-mentioned one or more of groups can specifically be used Close, when using polymer monomer, should polymerize monomer to form polymer with necessary heating or illumination methods.
Above-mentioned pixel cell can be prepared by the following procedure method and obtain:
First, first electrode is prepared.
First electrode pattern is prepared on the substrate with TFT drive circuits.The TFT drive circuits refer to Thin Film Transistor, i.e. thin film transistor (TFT).
2nd, pixel defining layer is prepared.
Pixel defining layer is prepared on aforesaid substrate and first electrode, and the pixel defining layer is formed by photoetching process Corresponding pixel hole.
3rd, light emitting functional layer and second electrode are prepared.
The light emitting functional layer and the second electrode are sequentially prepared out above first electrode in above-mentioned pixel hole, it is described Light emitting functional layer at least includes one layer of luminescent layer, and light emitting functional layer also includes hole injection layer, hole transmission layer, electronics if necessary Implanted layer, electron transfer layer;
1st, pre-treatment.
Before light emitting functional layer is prepared, pre-treatment can be carried out, it is specific as follows:
Substrate with first electrode and pixel defining layer is used in alkaline cleaner and ultra-pure water and is cleaned by ultrasonic, then Dried up, vacuum bakeout 30 minutes at 100 DEG C, handled 10 seconds with UV/ ozone with nitrogen.
2nd, light emitting functional layer and second electrode are prepared.
The top of first electrode in pixel is cheated, forms the electroluminescent hair of top emission type by way of inkjet printing and evaporation Optical device.The electroluminescent device of top emitting is collectively constituted by first electrode, light emitting functional layer and second electrode.At the top of wherein Second electrode be it is transparent or semitransparent, light emitting functional layer between two electrodes for one or more layers film organic material or Person's inorganic material film, at least containing one layer of luminescent layer, while can be comprising the one or more in following functions layer:Hole is injected Layer, hole transmission layer, electronic barrier layer, hole blocking layer, electron transfer layer, electron injecting layer etc..And first electrode is that have The metal Ag of reflex.
The structure of device is prepared in the following manner in one of the embodiments:
(1) hole injection layer:The example of hole injection layer material includes Amines, phthalocyanine compound, metal Oxide (such as tungsten oxide, molybdenum oxide, vanadium oxide), polythiophene class compound;Preferably, hole injection layer material is selected from aryl Aminated compounds.During preparation, hole-injecting material is dissolved in solvent ink is made, the solvent of the ink can include following solvent In at least two:Chloroform, toluene, dimethylbenzene, chlorobenzene, diphenyl ether, isopropanol, dimethylaniline, water.And by obtained hole Injection material ink is injected in pixel hole in inkjet printing mode, and uniform film-form knot is formed by vacuum drying, baking Structure, the thickness of the hole injection layer film is 5-150nm, and thickness preferably is 10-90nm.
(2) hole transmission layer:The example of hole mobile material includes polyaryl aminated compounds, polyarylamine and its derivative Thing, PVK and its derivative, polythiophene and its derivative;Preferably, hole transport layer material is selected from aryl amine Compound.Hole mobile material is dissolved in mixed solvent formation ink, and the solvent of the ink can be included in following instance at least Two kinds:Chloroform, tetrahydrofuran, ethyl acetate, toluene, dimethylbenzene, chlorobenzene, diphenyl ether, isopropanol, dimethylaniline.Hole is passed Defeated material ink is injected in pixel hole in inkjet printing mode, and the drawout on dry hole injection layer film passes through Vacuum drying, baking, form the hole transport layer film of covering hole injection layer, the thickness of hole transport layer film is 5- 150nm, thickness preferably is 15-60nm.
(3) luminescent layer:Luminescent layer includes small molecule and high molecular transmitting fluorescence, the organic material of phosphorescence, and quantum Point material etc..Luminescent layer can be made up of a kind of material, for example quantum dot light emitting material.Luminescent layer can also be by two kinds or two kinds Above material is constituted, and wherein at least includes a kind of material of main part, and including at least a kind of dopant material.The example of material of main part Including carbazole compound or polymer containing aromatic substituent, Benzophenanthrene compound or polymerization containing aromatic substituent Thing, containing fragrance substitution and benzothiophenes or polymer, the compound in triazine class containing aromatic substituent or poly- Compound etc.;Preferably, material of main part is selected from carbazole compound or polymer containing aromatic substituent, contains aromatic substituent Benzophenanthrene compound or polymer.The example of dopant material includes the compound containing Ir elements, the change containing Pt elements Compound, the compound containing Cu (I), the compound containing Os elements, delayed fluorescence class compound;Preferably, dopant material is selected From the metal complex of also Ir elements, the metal complex containing Pt elements, delayed fluorescence class compound.Emitting layer material is molten In mixed solvent formation ink, the solvent of the ink includes at least two in following instance:Chloroform, tetrahydrofuran, acetic acid Ethyl ester, toluene, dimethylbenzene, chlorobenzene, diphenyl ether, isopropanol, dimethylaniline.The ink of emitting layer material is in inkjet printing mode Inject in pixel hole, deploy on dry hole transport layer film upper berth, by vacuum drying, baking, formation is covered in Luminous layer film on hole transmission layer, the thickness for the layer film that lights is 10-100nm, and thickness preferably is 20-60nm.
(4) electron transfer layer:The example of electron transport material includes the compound containing aromatic substituent, is taken containing fragrance For Ji oxadiazole compounds, the quinone compounds containing aromatic substituent, the triaizine compounds containing aromatic substituent, 8- hydroxyls Base quinoline metal complex etc.;Preferably, electron transport layer materials are selected from the triaizine compounds containing aromatic substituent, 8- hydroxyls Quinoline metal complex.Electron transfer layer is prepared by the way of evaporation, and thickness is 10-60nm, and thickness preferably is 20- 50nm。
(5) second electrode:Transparent or semitransparent second electrode is conductive oxide (such as ITO, FTO, the oxidation of doping Zinc), sheet metal (alloys of such as Ag, Al, Mg or this several metal), or graphene.
4th, film layer is prepared.
In practice, for preparing film layer structure, it can be formed before encapsulation process, can also be after encapsulation process Formed, or transparent configuration is a part in encapsulating structure in itself.
The film layer is prepared above second electrode in above-mentioned pixel hole, can specifically be adopted with the following method:
Above-mentioned top emitting electroluminescent device is completed after preparing, in the pixel hole of pixel defining layer, with inkjet printing Or the mode of melting injection inserts solution state or process heating the transparent material that can be flowed.
The example of the transparent material includes following polymer or polymer monomer:PA (polyamide), PAN (polypropylene Cyanogen), PBT (polybutylene terephthalate (PBT)), PC (makrolon), PMMA (polymethyl methacrylate), PE (polyethylene), PES (poly- to benzene diethyl sulfone), PET (PET), PEN (PEN), PI (polyamides Asias Amine), PP (polypropylene), PS (polystyrene), PSO (polysulfones), PVC (polyvinyl chloride), silicone (polysiloxanes), PVDF (polyvinylidene fluoride), PVAc (polyvinyl acetate), Polyurea (polyureas), PTFE (polytetrafluoroethylene (PTFE)) and epoxy One or more of combinations in resin (epoxy resin).It should be understood that when using polymer monomer, Ying Yibi The heating or illumination methods wanted make monomer polymerize to form polymer.
Because pixel defining layer material surface has low surface tension, shape between transparent material and pixel defining layer material Into larger contact angle β, contact angle β's ranges preferably from 30 ° -90 °, so as to obtain the shape that surface raises up.Will be saturating Bright material is fully dried under vacuum conditions, and heating is aided with if necessary, fully to remove the moisture in transparent material, is produced described Film layer.
Specifically, the film layer can be formed by the way of inkjet printing and/or extrusion processing.
The concrete mode of the inkjet printing is:The solution of film layer material is inserted into pixel hole in the way of inkjet printing It is interior, it is covered on second electrode, then solvent is volatilized, and removes residual solvent and moisture.
It is preferred that, printed with ink-jet printer, and solvent is volatilized under the conditions of cryogenic vacuum, then again true Heated to remove residual solvent and moisture under empty condition;
It is described extrusion processing concrete mode be:The film layer material extrusion for heating fusing is inserted in pixel hole, covering On second electrode, temperature is set to be slowly dropped to room temperature.
It is preferred that, temperature slow cooling is made under vacuum conditions to room temperature.
The present inventor also has found that film layer has the dome top surface of radian and connecing for pixel defining layer surface under study for action The height of line is touched, can both be located at the inwall (such as Fig. 4) that pixel is cheated, the top (such as Fig. 2 and 3) that pixel is cheated can also be located at, is led to Cross the height of adjustment contact line, it is possible to adjust the radian of the bossing of film layer.When contact line is located at the inwall that pixel is cheated And when being also not up to the height at the top of pixel hole, with the change of height of contact wire, the radian of film layer upper surface will be protected substantially Hold constant, i.e., now the thickness change of film layer influences little to the radian of its upper surface.And when the height of contact line reaches picture During the overhead height in element hole, the upper surface of film layer is located at the angle between the tangent line at contact point and pixel defining layer upper surface α (Fig. 3) can be adjusted by the injection rate of transparent material, as long as angle α defines material list no more than transparent material in pixel The contact angle β in face, i.e., will not occur the spilling of transparent material solution.
Therefore, need to connecing film layer upper surface and pixel defining layer when needing to adjust the radian of film layer upper surface The height for touching line adjusts the radian for controlling its upper surface with the injection rate of transparent material to the top of pixel defining layer.
It should be understood that after the completion of prepared by above-mentioned film layer, can also further be sealed to whole display base plate or device Dress protection.For example, that is, on the whole display base plate including film layer structure, PECVD side can be used by the way of thin-film package Formula deposits 5nm-100 μm one or more layers encapsulating material, the example of encapsulating material include silicon nitride, silica, silicon oxynitride, One or more of combinations in organosilicon (polysiloxanes), aluminum oxide, zirconium oxide, aluminium nitride.
Embodiment
A kind of pixel cell, including:Substrate 100, first electrode 200, pixel defining layer 300, film layer, light emitting functional layer With second electrode 400, the first electrode 200 is located on the substrate 100, and the pixel defining layer 300 is formed at the base On plate 100 and the first electrode 200, and in the position corresponding with the first electrode 200 provided with receiving marking ink Pixel hole 310, the light emitting functional layer and second electrode 400 are cascadingly set in the pixel hole 310, and cover described First electrode 200, the base portion of the film layer 500 covers the second electrode, and the top of the film layer 500 has projection Radian, and the film layer 500 is made of clear material, the refractive index of the film layer 500 is more than air refraction and is less than The refractive index of the second electrode.
In the present embodiment, first electrode 200 is anode, and second electrode is negative electrode.
In the present embodiment, the top of the film layer 500 has a round and smooth radian of convex lens shape, the film layer 500 it is transparent The scope of contact angle β between material and the material of pixel defining layer 300 is 30 ° -90 °.Also, the inwall in the pixel hole is set to Angle is 10 ° -70 ° of slope.
Above-mentioned pixel cell can be prepared by the following procedure method and obtain:
First, first electrode is prepared.
The first electrode 200 with pattern of pixels is prepared on the substrate 100 with TFT drive circuits.
2nd, pixel defining layer is prepared.
Pixel defining layer 300 is prepared on aforesaid substrate 100 and first electrode 200, and the pixel is made by photoetching process Define layer and form corresponding pixel hole 310.
3rd, light emitting functional layer and second electrode 400 are prepared.
The top of first electrode 200 is sequentially prepared out the light emitting functional layer and second electrode in above-mentioned pixel hole 310 400, the light emitting functional layer at least includes one layer of luminescent layer, as shown in Figure 1.
1st, pre-treatment.
Before light emitting functional layer is prepared, pre-treatment can be carried out, it is specific as follows:
Substrate with first electrode and pixel defining layer is used in alkaline cleaner and ultra-pure water and is cleaned by ultrasonic, then Dried up, vacuum bakeout 30 minutes at 100 DEG C, handled 10 seconds with UV/ ozone with nitrogen.
2nd, light emitting functional layer and second electrode are prepared.
The top of first electrode in pixel is cheated, forms the electroluminescent hair of top emission type by way of inkjet printing and evaporation Optical device.The electroluminescent device of top emitting is collectively constituted by pixel first electrode, light emitting functional layer and second electrode.Wherein push up The second electrode in portion is transparent or semitransparent, and the light emitting functional layer between two electrodes is organic material of one or more layers film Material or inorganic material film, at least containing one layer of luminescent layer, while can be comprising the one or more in following functions layer:Hole Implanted layer, hole transmission layer, electronic barrier layer, hole blocking layer, electron transfer layer, electron injecting layer etc..And first electrode is Metal Ag with reflex.
In the present embodiment, the structure of device is prepared in the following manner:
(1) hole injection layer:Hole injection layer material is Amines.It is during preparation, hole-injecting material is molten Ink is made in solvent, the solvent of the ink preferably is selected from toluene, dimethylbenzene, chlorobenzene, diphenyl ether, dimethylaniline at least Two kinds.And inject obtained hole-injecting material ink in pixel hole in inkjet printing mode, by vacuum drying, baking Uniform film like structures are formed, the thickness of the hole injection layer film is 90nm.
(2) hole transmission layer:Hole mobile material is also selected from polyaryl aminated compounds.Hole mobile material is dissolved in mixing Solvent formation ink, the solvent of the ink preferably is selected from tetrahydrofuran, ethyl acetate, toluene, dimethylbenzene, chlorobenzene, diphenyl ether, two At least two in methylaniline.Hole mobile material ink is injected in pixel hole in inkjet printing mode, what is dried Drawout on hole injection layer film, by vacuum drying, baking, forms the hole transport layer film of covering hole injection layer, The thickness of hole transport layer film is 60nm.
(3) luminescent layer:The material of main part of luminescent layer is selected from carbazole compound or polymer containing aromatic substituent, with And Benzophenanthrene compound or polymer containing aromatic substituent.Dopant material is selected from the compound containing Ir elements.It is luminous Layer material is dissolved in mixed solvent formation ink, and the solvent of the ink is selected from tetrahydrofuran, ethyl acetate, toluene, dimethylbenzene, chlorine Benzene, diphenyl ether, isopropanol, dimethylaniline.The ink of emitting layer material is injected in pixel hole in inkjet printing mode, Dry hole transport layer film upper berth expansion, by vacuum drying, baking, forms the luminescent layer being covered on hole transmission layer Film, the thickness for the layer film that lights is 60nm.
(4) electron transfer layer:Electron transport material is selected from the triaizine compounds containing aromatic substituent and 8- hydroxyl quinolines Quinoline metal complex.Electron transfer layer is prepared by the way of evaporation, and thickness is 45nm.
(5) second electrode:Second electrode is the ITO prepared using sputtering mode, and thickness is 50nm.
4th, film layer is prepared.
The film layer is prepared above second electrode in above-mentioned pixel hole, as shown in Figures 2 and 3, specifically can be using such as Lower method:
Above-mentioned top emitting electroluminescent device is completed after preparing, in being cheated by the pixel of pixel defining layer, with printing Mode injects solution state or process heating the transparent material that can be flowed.
The example of the transparent material includes following polymer or polymer monomer:PA (polyamide), PAN (polypropylene Cyanogen), PBT (polybutylene terephthalate (PBT)), PC (makrolon), PMMA (polymethyl methacrylate), PE (polyethylene), PES (poly- to benzene diethyl sulfone), PET (PET), PEN (PEN), PI (polyamides Asias Amine), PP (polypropylene), PS (polystyrene), PSO (polysulfones), PVC (polyvinyl chloride), silicone (polysiloxanes), PVDF (polyvinylidene fluoride), PVAc (polyvinyl acetate), Polyurea (polyureas), PTFE (polytetrafluoroethylene (PTFE)) and epoxy One or more of combinations in resin (epoxy resin).
More specifically, (poly- selected from PC (makrolon), PE (polyethylene), PET (polyethylene terephthalate), PEN (ethylene naphthalate)), PP (polypropylene), PVC (polyvinyl chloride), silicone (polysiloxanes).It should be understood that working as makes When being polymer monomer, it should polymerize monomer to form polymer with necessary heating or illumination methods.
Because pixel defining layer material surface has low surface tension, shape between transparent material and pixel defining layer material Into larger contact angle β, contact angle β is in the range of 30 ° -90 °, preferably 45 ° -90 °, more specifically can be controlled in 45 ° - In the range of 60 °, so as to obtain the shape that surface raises up.Transparent configuration is fully dried under vacuum conditions, it is auxiliary if necessary To heat, fully to remove the moisture in transparent configuration, the film layer is produced.
Specifically, the film layer is formed by the way of extrusion injection.
The extrusion injects the concrete mode processed:The film layer material extrusion for heating fusing is inserted in pixel hole, It is covered on second electrode, slow cooling is to room temperature under vacuum conditions.
The present inventor also has found that film layer has the dome top surface of radian and connecing for pixel defining layer surface under study for action The height of line is touched, can both be located at the inwall (such as Fig. 4) that pixel is cheated, the top (such as Fig. 2 and 3) that pixel is cheated can also be located at, is led to Cross the height of adjustment contact line, it is possible to adjust the radian of the bossing of film layer.When contact line is located at the inwall that pixel is cheated And when being also not up to the height at the top of pixel hole, with the change of height of contact wire, the radian of film layer upper surface will be protected substantially Hold constant, i.e., now the thickness change of film layer influences little to the radian of its upper surface.And when the height of contact line reaches picture During the overhead height in element hole, the upper surface of film layer is located at the angle between the tangent line at contact point and pixel defining layer upper surface α (Fig. 3) can be adjusted by the injection rate of transparent material, as long as angle α defines material list no more than transparent material in pixel The contact angle β in face, i.e., will not occur the spilling of transparent material solution.
Therefore, need to connecing film layer upper surface and pixel defining layer when needing to adjust the radian of film layer upper surface The height for touching line adjusts the radian for controlling its upper surface with the injection rate of transparent material to the top of pixel defining layer.
In the present embodiment, the width of single pixel is 60 μm, and the contact line of transparent material and pixel defining layer is located at picture Element defines layer top in pixel hole, and contact angle β of the transparent material on pixel defining layer surface is 50 °, and angle α is 45 °, transparent knot The thickness of structure is about 50 μm.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, the scope of this specification record is all considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and it describes more specific and detailed, but simultaneously Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that coming for one of ordinary skill in the art Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (10)

1. a kind of pixel cell of printed form electroluminescent device, including:Substrate, first electrode, pixel defining layer, lighting function Layer and second electrode, the first electrode are located on the substrate, and the pixel defining layer is formed at the substrate and described the On one electrode, and in the position corresponding with the first electrode provided with the pixel hole for accommodating marking ink, it is characterised in that
Also include film layer, the light emitting functional layer and the second electrode are cascadingly set in the pixel hole, and are covered The first electrode is covered, the base portion of the film layer covers the second electrode, and the top of the film layer has raised arc Spend, and the film layer is made of clear material, the refractive index of the film layer is more than air refraction and less than described second The refractive index of electrode.
2. the pixel cell of printed form electroluminescent device according to claim 1, it is characterised in that the pixel hole Inwall is the slope that angle is 10 ° -70 °.
3. the pixel cell of printed form electroluminescent device according to claim 2, it is characterised in that the film layer The scope of contact angle β between transparent material and the pixel defining layer material is 30 ° -90 °.
4. the pixel cell of printed form electroluminescent device according to claim 1, it is characterised in that the film layer bag Include the sandwich construction that at least two different refractivity materials are made, and the refractive index per Rotating fields on the direction away from substrate by Gradually reduce.
5. the pixel cell of printed form electroluminescent device according to claim 1, it is characterised in that the film layer is most Big thickness is not less than 0.5 μm.
6. the pixel cell of the printed form electroluminescent device according to claim any one of 1-5, it is characterised in that described Film layer is made up of at least one of following material:It is organic molecule of the molecular weight less than 2000, organic polymer resin, organic Silicon, metal oxide, metal sulfide, Si oxide, silicon oxynitride and silicon nitride.
7. the pixel cell of printed form electroluminescent device according to claim 6, it is characterised in that the film layer by At least one of following material is made:Polyamide, polypropylene cyanogen, polybutylene terephthalate (PBT), makrolon, poly- methyl It is methyl acrylate, polyethylene, poly- sub- to benzene diethyl sulfone, PET, PEN, polyamides Amine, polypropylene, polystyrene, polysulfones, polyvinyl chloride, polysiloxanes, polyvinylidene fluoride, polyvinyl acetate, polyureas, poly- four PVF and epoxy resin.
8. the preparation method of the pixel cell of the printed form electroluminescent device described in claim any one of 1-7, its feature exists In comprising the following steps:
Prepare first electrode:First electrode pattern is prepared on the substrate with TFT drive circuits;
Prepare pixel defining layer:Pixel defining layer is prepared on aforesaid substrate and first electrode, and the picture is made by photoetching process Element defines layer and forms corresponding pixel hole;
Prepare light emitting functional layer and second electrode:In above-mentioned pixel hole the lighting function is sequentially prepared out above first electrode Layer and the second electrode, the light emitting functional layer at least include one layer of luminescent layer;
Prepare film layer:In above-mentioned pixel hole the film layer is prepared above second electrode.
9. the preparation method of the pixel cell of printed form electroluminescent device according to claim 8, it is characterised in that institute State in preparation film layer step, the film layer is formed by the way of inkjet printing and/or extrusion processing;
The concrete mode of the inkjet printing is:The solution of film layer material is inserted in the way of inkjet printing in pixel hole, It is covered on second electrode, then solvent is volatilized, and removes residual solvent and moisture;
It is described extrusion processing concrete mode be:The film layer material extrusion for heating fusing is inserted in pixel hole, the is covered in On two electrodes, temperature is set to be slowly dropped to room temperature.
10. a kind of light-emitting display device, it is characterised in that the picture with the printed form electroluminescent device described in any one of 1-7 Plain unit.
CN201610695573.XA 2016-08-19 2016-08-19 Pixel cell of printed form electroluminescent device and its preparation method and application Pending CN107046047A (en)

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