CN106252528A - The manufacture method of luminescent device, luminescent device and mixed luminescence device - Google Patents
The manufacture method of luminescent device, luminescent device and mixed luminescence device Download PDFInfo
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- CN106252528A CN106252528A CN201610738773.9A CN201610738773A CN106252528A CN 106252528 A CN106252528 A CN 106252528A CN 201610738773 A CN201610738773 A CN 201610738773A CN 106252528 A CN106252528 A CN 106252528A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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Abstract
The invention provides the manufacture method of a kind of luminescent device, luminescent device and mixed luminescence device.This manufacture method comprises the following steps: step S1, is arranged on substrate by the mask plate with multiple hollow-out parts;Step S2, uses solwution method to make ink be arranged at the surface of substrate by hollow-out parts;Step S3, by the ink dried of substrate surface, forms luminescent layer or functional layer.Owing to this manufacture method is by being arranged on substrate by the mask plate with multiple hollow-out parts, solwution method is used to make ink be arranged at the surface of substrate by hollow-out parts again, then by the ink dried of substrate surface, form luminescent layer or functional layer, thus utilize mask plate to block the ink dispersion to other color regions, efficiently avoid the generation of colour mixture problem, improve the color accuracy of luminescent device.
Description
Technical field
The present invention relates to optical technical field, in particular to the manufacture method of a kind of luminescent device, luminescent device and
Mixed luminescence device.
Background technology
Along with the development of science and technology, the requirement of display image quality is constantly promoted by people, QLED (quantum dot light emitting
Diode) show that with its high color purity, color saturation and wide colour gamut be considered as the most representational Display Technique in future.
At present QLED device mainly utilizes solwution method processing procedure to make, such as inkjet printing, silk screen printing, spin coating, slot coated etc., due to
The pixel of display is the least, and the coating of current sub-pixel typically utilizes InkJet printing processes selectively applied to carry out, and is i.e. having
In the RGB sub-pixel groove that pixel isolation structure is constructed, nozzle is utilized to print R, G, B quantum dot ink successively.Due to the most blue
Light QLED device inefficient, directly utilizes quantum dot and constructs the QLED device that RGB shows and also acquire a certain degree of difficulty, and traditional
The blue light development of LED Yu OLED is more ripe, therefore can utilize RG photic combination LED or the OLED blue light electroluminescence of quantum dot
Realize the mode that RGB shows, can comparatively fast realize in a short time.
But, in above-mentioned InkJet printing processes, the droplet morphology of nozzle ejection is highly unstable, usually in main droplet week
Enclosing it is observed that the most tiny drop, dispersion droplet out easily deviates original position, drops into nearby subpixels
In region, thus in causing each sub-pixel, the material amount of falling into is different or the generation of colour mixture problem, and then have impact on luminescent device
Whole performance or generation aberration, reduce the yield of product.
Summary of the invention
Present invention is primarily targeted at and the manufacture method of a kind of luminescent device, luminescent device and mixed luminescence device are provided
Part, to solve the problem that luminescent device of the prior art causes aberration due to colour mixture.
To achieve these goals, according to an aspect of the invention, it is provided the manufacture method of a kind of luminescent device, wrap
Include following steps: step S1, the mask plate with multiple hollow-out parts is arranged on substrate;Step S2, uses solwution method to make ink
Water is arranged at the surface of substrate by hollow-out parts;Step S3, by the ink dried of substrate surface, forms luminescent layer or functional layer.
Further, ink is quanta point material ink, and manufacture method also includes at least being repeated once step S1's to S3
Process, in each repetitive process, the zones of different of the hollow-out parts counterpart substrate of the mask plate used, sending out of the ink used
Light color is the most different.
Further, the mask plate in step S1 has modified surface, modified surface include mask plate away from substrate
One side surface, modified surface has hydrophilic or hydrophobicity;The ink that step S2 is used has different close and distant from modified surface
Aqueous.
Further, modified surface also includes the side surface of close substrate of mask plate.
Further, when modified surface is hydrophobic surface, manufacture method also include formed modified surface process: step
S01, immerses in the solution with hydrophobic material, so that hydrophobic material is fixed on the surface of mask plate, preferably by mask plate
Hydrophobic material is fluorine-containing silane coupler;Step S02, will be fixed with mask plate and the solution separating of hydrophobic material, and
Mask plate is dried process, to be formed, there is hydrophobic modified surface.
Further, manufacture method also includes the process that mask plate carries out pretreatment, and the process of pretreatment includes: to covering
The surface of template carries out ultraviolet and ozone photodissociation oxidation, so that the hydrophilic surface of mask plate is the most exposed.
Further, the substrate in step S1 has a pixel isolation structure, and pixel isolation structure have multiple mutually every
From subpixel area, the corresponding each subpixel area of hollow-out parts is arranged;Step S2 makes ink pass through hollow-out parts and enters corresponding son
In pixel region.
Further, the surface of the substrate in step S1 has hydrophilic region and hydrophobic region, hollow-out parts correspondence hydrophilic area
Territory or hydrophobic region are arranged;Step S2 makes hydrophobic ink be entered in hydrophobic region by hollow-out parts, or makes hydrophilic ink
Water is entered in hydrophilic region by hollow-out parts.
Further, ink is hole-injecting material ink, hole mobile material ink, electron injection material ink and electricity
Any one in sub-transport layer material ink, in step s3, by ink dried, to form the hole injection layer of correspondence, hole
Transport layer, electron injecting layer or electron transfer layer;Or ink is quanta point material ink or luminous organic material ink, in step
In S3, by ink dried, to form corresponding quantum dot light emitting layer or organic luminous layer.
Further, step S2 use spraying coating process or InkJet printing processes so that ink is arranged at base by hollow-out parts
The surface of plate, spraying coating process is preferably ultrasonic spraying.
According to a further aspect in the invention, it is provided that a kind of luminescent device, luminescent device prepared by above-mentioned manufacture method and
Becoming, luminescent device is electroluminescent device or photo luminescent devices.
According to a further aspect in the invention, additionally providing a kind of mixed luminescence device, luminescent device includes electroluminescent cell
Part and be arranged at the photo luminescent devices of electroluminescent device light emission side, electroluminescent device and/or photo luminescent devices are
Manufacture method is prepared from.
Application technical scheme, it is provided that the manufacture method of a kind of luminescent device, owing to this manufacture method is logical
Cross and the mask plate with multiple hollow-out parts is arranged on substrate, then use solwution method to make ink be arranged at substrate by hollow-out parts
Surface, then by the ink dried of substrate surface, form luminescent layer or functional layer, thus utilize mask plate block ink to
The dispersion of other color regions, efficiently avoid the generation of colour mixture problem, improves the color accuracy of luminescent device.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is further detailed explanation.
Accompanying drawing explanation
The Figure of description of the part constituting the present invention is used for providing a further understanding of the present invention, and the present invention shows
Meaning property embodiment and explanation thereof are used for explaining the present invention, are not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the schematic flow sheet of the manufacture method of the luminescent device that embodiment of the present invention provided.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the present invention and the feature in embodiment can phases
Combination mutually.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
In order to make those skilled in the art be more fully understood that the present invention program, below in conjunction with in the embodiment of the present invention
Accompanying drawing, is clearly and completely described the technical scheme in the embodiment of the present invention, it is clear that described embodiment is only
The embodiment of a present invention part rather than whole embodiments.Based on the embodiment in the present invention, ordinary skill people
The every other embodiment that member is obtained under not making creative work premise, all should belong to the model of present invention protection
Enclose.
It should be noted that term " first " in description and claims of this specification and above-mentioned accompanying drawing, "
Two " it is etc. for distinguishing similar object, without being used for describing specific order or precedence.Should be appreciated that so use
Data can exchange in the appropriate case, in order to embodiments of the invention described herein.Additionally, term " includes " and " tool
Have " and their any deformation, it is intended that cover non-exclusive comprising, such as, contain series of steps or unit
Process, method, system, product or equipment are not necessarily limited to those steps or the unit clearly listed, but can include the most clear
That list to Chu or for intrinsic other step of these processes, method, product or equipment or unit.
As described in background technology, ink droplets dispersion after spraying due to nozzle in existing InkJet printing processes,
Dispersion droplet out easily deviates original position, falls in the region of other colors, thus causes the product of colour mixture problem
Raw, and then have impact on the final color of luminescent device and produce aberration.Present inventor studies for the problems referred to above,
Propose the manufacture method of a kind of luminescent device, as it is shown in figure 1, comprise the following steps: step S1, will there is multiple hollow-out parts
Mask plate is arranged on substrate;Step S2, uses solwution method to make ink be arranged at the surface of substrate by hollow-out parts;Step S3,
By the ink dried of substrate surface, form luminescent layer or functional layer.
The above-mentioned manufacture method of the present invention, by being arranged on substrate by the mask plate with multiple hollow-out parts, and makes to engrave
Target area on sky portion counterpart substrate, the nontarget area on substrate can the hollow-out parts of corresponding mask plate can also correspondence be covered
The non-hollow-out parts of template, then use solwution method to make ink be arranged at the surface of substrate by hollow-out parts, then by substrate surface
Ink dried, forms luminescent layer or functional layer, thus utilizes mask plate to block the ink dispersion to other color regions, especially
It is that quantum dot ink spreads to other adjacent domains, efficiently avoid the generation of colour mixture problem, improve the color of luminescent device
Color degree of accuracy.
The illustrative embodiments of manufacture method of the luminescent device provided according to the present invention is provided.
But, these illustrative embodiments can be implemented by multiple different form, and should not be construed to be limited solely to this
In the embodiment that illustrated.It should be appreciated that these embodiments are provided so that disclosure herein thoroughly and
Completely, and by the design of these illustrative embodiments it is fully conveyed to those of ordinary skill in the art.
Ink in the application can be hole-injecting material ink, hole mobile material ink, electron injection material ink
Any one in water and electron transport layer materials ink, in step s3, by ink dried, to form corresponding hole injection
Layer, hole transmission layer, electron injecting layer or electron transfer layer;Or ink is quanta point material ink or luminous organic material ink
Water, in step s3, by ink dried, to form corresponding quantum dot light emitting layer or organic luminous layer.Further, in order to make luminescence
Device can have the emergent light of shades of colour, and the quantum dot in the most above-mentioned quanta point material ink is independently selected from amount of red
Any one in sub-point, blue quantum dot and green quantum dot.
When above-mentioned ink is quanta point material ink, after performing step S3, manufacture method can also include at least
It is repeated once the process of step S1 to S3, in each repetitive process, the difference of the hollow-out parts counterpart substrate of the mask plate used
Region, the glow color of the ink used is the most different.By arranging the amount of different glow color on the target area of substrate
Son point material ink is also dried, the glow color final to adjust luminescent device;Further, by the diverse location at substrate surface
On red quantum point and green quantum dot are set, under the irradiation of Blue backlight, this luminescent device can realize red and green
Luminescence generated by light, thus realize the full-color display of RGB.
Further, according to the difference of material category, above-mentioned ink can be divided into hydrophilic inks and hydrophobicity ink.Wherein,
When above-mentioned quanta point material ink is hydrophilic inks, above-mentioned hydrophilic inks includes hydrophilic quantum dot, and hydrophilic amount
Son point contains the quantum dot of hydrophilic group for surface ligand, and preferably hydrophilic group is carboxyl, amino, hydroxyl or sulfydryl;When above-mentioned amount
When son point material ink is hydrophobicity ink, above-mentioned hydrophobicity ink includes hydrophobicity quantum dot, and hydrophobicity quantum dot is table
The face part quantum dot containing hydrophobic group, preferably hydrophobic group is alkane chain or ester group.
Above-mentioned there is hydrophilic or hydrophobic quanta point material ink can also include curable resin or monomer whose with
And solvent (or referred to as dispersant).Wherein, solvent can be long chain hydrocarbon, alcohol, ester and the ether between 40~250 DEG C selected from boiling point
Mixture is as organic solvent.Preferably, hydrocarbon is straight or branched alkane, and such as, hydrocarbon is C6-10 alkane.Organic solvent is permissible
For chlorobenzene, o-dichlorohenzene, oxolane, methyl phenyl ethers anisole, morpholine, toluene, o-Dimethylbenzene, meta-xylene, xylol, alkylbenzene,
Nitrobenzol, normal hexane, hexamethylene, normal heptane, cycloheptane, dioxane, dichloromethane, chloroform, dichloroethanes, chloroform,
Chlorobenzene, 1,4 dioxanes, 1,2 dichloroethanes, 1,1,1-trichloroethane, 1,1,2,2-sym-tetrachloroethane, naphthane, naphthalane,
N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide chloroform, oxolane, dichloromethane, toluene, just oneself
Alkane, methanol, ethanol, propanol, butanol, acetone, dioxane, dimethylformamide and dimethyl sulfoxide.Wherein, curable resin
Monomer crosslinked formation curable resin selected from epoxy resin, acrylic resin, organic siliconresin, or correspondence.Above-mentioned hydrophilic
Property and hydrophobicity quantum dot ink can also include the cross-linking agent of band double bond, light curing agent or thermal curing agents etc..
In a preferred embodiment, the mask plate in step S1 has modified surface, and modified surface includes mask
A side surface away from substrate of plate, modified surface has hydrophilic or hydrophobicity;The ink that step S2 is used and modified table
Mask has different hydrophilic and hydrophobic.By making hydrophobicity ink be arranged by the hollow-out parts with the mask plate on hydrophilically modified surface
Correspondence position on substrate, or make hydrophilic inks be arranged at by the hollow-out parts with the mask plate on hydrophobic modified surface
Correspondence position on substrate, it is possible to make ink to stick on mask plate, thus improve the guidance quality of material, and then not only
The spraying coating process in solwution method can be utilized to make pixel, additionally it is possible to utilize the relatively low ink jet printing device of precision to make picture
Element, reduces the cost used needed for accurate ink jet printing device.
Above-mentioned preferred embodiment in, in order to utilize mask plate to improve the guidance quality of material further, be more highly preferred to
Ground, modified surface also includes a side surface of the close substrate of mask plate.By making the side of the close substrate of mask plate also have
There is modified surface, and modified surface has different hydrophilic and hydrophobic from ink, it is possible to make that there is hydrophilic or hydrophobic ink exists
Will not stick to when hollow-out parts is passed through near a side surface of substrate.
Prior art typically uses the material of metal material or other hydrophilic ultraviolet aging resistances to prepare mask plate.Due to gold
The oxide layer of metal surface can be the most affine with water such that it is able to it is all hydrophilic for making major part metal surface, and then can make
The correspondence position that hydrophobicity ink can be arranged on substrate by the hollow-out parts of aforementioned mask plate, changes without sticking to surface
On property mask plate, and then improve the guidance quality of hydrophobic material.
In order to obtain the mask plate with hydrophobic modified surface, it is preferable that above-mentioned manufacture method is additionally included in mask plate
The process of upper formation modified surface: step S01, immerses mask plate in the solution with hydrophobic material, so that hydrophobicity material
Material is fixed on the surface of mask plate;Step S02, will be fixed with mask plate and the solution separating of hydrophobic material, and to mask plate
It is dried process, to be formed, there is hydrophobic modified surface.Hydrophilic ink preferred embodiment can be made by above-mentioned
The correspondence position that water is arranged on substrate by the hollow-out parts of aforementioned mask plate, without sticking on surface modification mask plate,
And then improve the guidance quality of hydrophilic material.In order to make the mask plate being prepared from have more preferable hydrophobicity, the most hydrophobic
Property material is fluorine-containing silane coupler.
Additionally, for the hydrophilic making full use of mask plate, it is preferable that the process forming modified surface includes: to mask
Plate surface carries out ultraviolet and ozone photodissociation oxidation, has hydrophilic modified surface to be formed.By mask plate surface is carried out
Ultraviolet and ozone photodissociation aoxidizes, the various greasy dirts of mask plate remained on surface, chemical substance to be removed and to expose hydrophilic metal
Surface, thus obtain the mask plate with hydrophilically modified surface.The process conditions ability of above-mentioned ultraviolet and ozone photodissociation oxidation
Field technique personnel can be set according to prior art.
The most exposed, therefore in above-mentioned steps S2 owing to have employed the surface of mask plate or the mask plate with modified surface
Spraying coating process or InkJet printing processes can be used so that ink is arranged at the surface of substrate by hollow-out parts.The most above-mentioned hydrophilic
Property ink or the viscosity≤50cps of hydrophobicity ink, to ensure that equipment shower nozzle can well control ink and go out liquid;Further, in order to
Ensure that ink mist can effectively be melted by shower nozzle, it is preferable that above-mentioned spraying coating process is ultrasonic spraying, and the most hydrophilic in order to improve
Property ink or the spraying effect of hydrophobicity ink, the supersonic frequency that the most ultrasonic spraying uses is 45kHz~180kHz, preferably parent
Water-base ink or the viscosity≤10cps of hydrophobicity ink.
In a preferred embodiment, the substrate in step S1 has pixel isolation structure, and pixel isolation structure
Having multiple mutually isolated subpixel area, the corresponding each subpixel area of hollow-out parts is arranged;Step S2 makes ink pass through hollow out
Portion enters in corresponding subpixel area.Above-mentioned pixel isolation structure can be effectively prevented the ink that different subpixel is interregional
Colour mixture, improves color accuracy.
In order to reduce due to when large area prepares luminescent device mask plate deformation and cause ink to fall into corresponding sub-pixel district
Amount or position there is deviation thus impact that color accuracy is brought, aforementioned mask plate can with substrate have pixel every
A side surface contact from structure is arranged;Further, in order to make hydrophilic inks or the hydrophobicity ink hollow-out parts by mask plate
Enter more accurately in the subpixel area of pixel isolation structure, it is preferable that the area of above-mentioned hollow-out parts is less than or equal to correspondence
The area of subpixel area, it is further preferable that hollow-out parts is consistent with the shape of corresponding subpixel area.
It is further preferable that the exposed surface of pixel isolation structure includes hydrophilic surface or hydrophobic surface.When above-mentioned picture
When the exposed surface of element isolation structure is hydrophilic surface, in step s 2, hydrophobicity ink is made to be arranged at base by hollow-out parts
The surface of plate;When the exposed surface of above-mentioned pixel isolation structure is hydrophobic surface, in step s 2, make hydrophilic inks
The surface of substrate it is arranged at by hollow-out parts, thus by making the surface of above-mentioned pixel isolation structure have different parents from ink
Hydrophobicity, can make in the step forming luminescent layer or functional layer ink will not remain in pixel isolation structure upper surface or
Person's sidewall, but be back in pixel region under gravity, and then the colour mixture being effectively prevented between adjacent pixel regions.
When the above-mentioned manufacture method using the present invention makes photo luminescent devices, in another preferred embodiment
In, the surface of the substrate in step S1 has hydrophilic region and hydrophobic region, and hollow-out parts correspondence hydrophilic region or hydrophobic region set
Put;Step S2 makes hydrophobic ink be entered in hydrophobic region by hollow-out parts, or makes hydrophilic ink be entered by hollow-out parts
Enter in hydrophilic region.Above-mentioned hydrophilic region and hydrophobic region can make to form multiple son being separated on the surface of transparent substrates
Pixel region, makes hydrophilic quantum dot ink enter hydrophilic region, and hydrophobic region is as isolation structure, or makes hydrophobic quantum
Point ink enters hydrophobic region, and hydrophilic region is as isolation structure, thus effectively prevent the amount that different subpixel is interregional
Son point ink blending, improves color accuracy;Further, compare the making side of pixel isolation structure is set on the transparent substrate
Method, the above-mentioned subpixel area that preferred embodiment can not only similarly make needed for ink injection, also reduce light simultaneously
The cost of manufacture of electroluminescence device.
It is further preferable that form multiple hydrophilic region and multiple hydrophobic region on a surface of a substrate, and each hydrophilic region
Alternately arranged with each hydrophobic region.Use above-mentioned can be formed on the surface of transparent substrates the most equally multiple
Mutually isolated subpixel area, thus by the quantum dot ink of different colours is had respectively entered different subpixel area
In, make above-mentioned quantum dot can form light emitting array under the irradiation of Blue backlight, and then prepared photo luminescent devices realizes RGB
Full-color display.
Above-mentioned preferred embodiment in, in order to make hydrophilic inks or the hydrophobicity ink hollow-out parts by mask plate
Enter more accurately in hydrophilic or the hydrophobicity subpixel area of substrate, it is further preferable that the area of the hollow-out parts of mask plate
Less than or equal to corresponding hydrophilic region or the area of hydrophobic region;The hollow-out parts of mask plate and corresponding hydrophilic region or hydrophobic region
The shape in territory is consistent.
The preparation method of the above-mentioned substrate with hydrophilic region and hydrophobic region may comprise steps of: step S001,
Surface configuration at substrate includes the raw material of the first reaction raw materials;Step S002, the first reaction that covering is positioned at first area is former
Material, and the first reaction raw materials being pointed to second area carries out ultraviolet light irradiation, the first reaction raw materials forms the at second area
Two masked areas;Step S003, removes the first reaction raw materials of first area, arranges on first area and the second masked areas
Second reaction raw materials;Step S004, hides and is positioned at the second reaction raw materials of the second masked areas, and is pointed to the of first area
Two reaction raw materials carry out ultraviolet light irradiation, and the second reaction raw materials forms the first masked areas in first area, then removes second
The second reaction raw materials in masked areas, wherein, the first reaction raw materials and the second reaction raw materials select hydrophilic reactant and dredge
Aqueous reactant, and the close and distant performance of the two is contrary, the first masked areas and the second corresponding hydrophilic region of masked areas and hydrophobic
Region.
In the preparation method of aforesaid substrate, the above-mentioned raw material including the first reaction raw materials can also include solvent, coupling
Agent and initiator.Now, above-mentioned steps S001 includes procedure below: A, coupling agent and initiator is mixed in a solvent, is formed
Processing substrate liquid;B, at least one side surface of substrate is positioned in processing substrate liquid, makes coupling agent bonding be fixed on printing opacity base
On the surface of plate and form bonding surface;C, the first reaction raw materials is arranged at bonding surface.In above-mentioned steps S002, pass through
The first reaction raw materials being pointed to second area carries out ultraviolet light irradiation, so that the first reaction raw materials and coupling agent are at ultra-vioket radiation
Under carry out graft reaction, thus form above-mentioned second masked areas;In above-mentioned steps S004, by being pointed to first area
Second reaction raw materials carries out ultraviolet light irradiation, so that the second reaction raw materials and coupling agent carry out graft reaction under ultra-vioket radiation,
Thus form above-mentioned first masked areas.
In the preparation method of aforesaid substrate, the process of the first reaction raw materials removing first area may include that with molten
Agent washes away the first reaction raw materials on first area, then the surface of substrate is dried process;Similarly, the second screening is removed
The process of the second reaction raw materials on cover region territory includes: wash away the second reaction raw materials in the second masked areas with solvent, then
The surface of substrate is dried process.Those skilled in the art can be according to the above-mentioned cleaning of prior art and dried
Process conditions be set.
In order to make between the first reaction raw materials and coupling agent and the second reaction raw materials is preferably grafted with coupling agent
Reaction, it is preferable that the formula of above-mentioned coupling agent is (X1-X2-X3-) Si-Y, wherein, Y is the group with vinyl or end strips
The alkyl of SH base, X1、X2And X3Separately selected from Cl, CH3、OCH3、OCH2CH3And CH2CH3In any one, and X1、X2With
X3It it is asynchronously alkyl;The formula of above-mentioned first reaction raw materials and the second reaction raw materials is A-B, and wherein, A is with vinyl
Group, now Y is the alkyl of end strips SH base, or the alkyl that A is end strips SH base, and now Y is the group with vinyl, B
For the residue of band hydrophilic group, now the first reaction raw materials or the second reaction raw materials are hydrophilic reactant, preferably hydrophilic group
For any one or more in sulfonic group, amido, hydroxyl, carboxyl and amino, or the residue that B is band hydrophobic group, now first
Reaction raw materials or the second reaction raw materials be hydrophobicity reactant, preferably hydrophilic group be in alkyl, ester group, halogen and nitro appoint
One or more.
The above-mentioned manufacture method of the present invention may also be used for making appointing in the luminescent layer of electroluminescent device or functional layer
One or more layers, now, aforesaid substrate is the first electrode base board, and, when forming luminescent layer in above-mentioned steps S3, preferably
Ground, after step s 3, manufacture method also includes step S4: arrange second in the side away from the first electrode base board of luminescent layer
Electrode.Use above-mentioned preferred embodiment can form that structure is the first electrode base board/luminescent layer/the second electrode electroluminescent
Optical device;When forming functional layer in step s3, it is preferable that after step s 3, manufacture method also includes step S4: function
Layer is the first implanted layer or the first transport layer, sets in the side away from the first electrode base board of the first implanted layer or the first transport layer
Put luminescent layer, and the second electrode is set in the side away from the first electrode base board of luminescent layer.Use above-mentioned preferred embodiment party
Formula can form the electroluminescent device with functional layer.
Above-mentioned preferred embodiment in, when the functional layer formed in step s3 is the first implanted layer, the most excellent
Selection of land, in step s 4, manufacture method also includes procedure below: before arranging the process of luminescent layer, repeats step S1 to S3,
With surface configuration the first transport layer at the first implanted layer;After the process that luminescent layer is set, repeat step S1 to S3, with
Surface configuration second transport layer of luminescent layer;And after the process that luminescent layer is set, repeat step S1 to S3, with second
Surface configuration second implanted layer of transport layer.Use above-mentioned preferred embodiment can be formed structure be the first electrode base board/
The electroluminescent device of the first implanted layer/the first transport layer/luminescent layer/the second transport layer/the second implanted layer/the second electrode.
In above-mentioned electroluminescent device, when the first electrode is anode, when the second electrode is negative electrode, the first implanted layer is
Hole injection layer, the first transport layer is hole transmission layer, and the second implanted layer is electron injecting layer, and the second transport layer is electric transmission
Layer;And when the first electrode is negative electrode, and when the second electrode is anode, the first implanted layer is electron injecting layer, the first transport layer is electricity
Sub-transport layer, the second implanted layer is hole injection layer, and the second transport layer is hole transmission layer, to form transoid electroluminescent cell
Part.
It is however noted that, in electroluminescent device, the preparation technology of each layer is not limited to above-mentioned preferred enforcement
Mode, those skilled in the art can prepare other each layer of electroluminescent device in conjunction with common process of the prior art.
According to further aspect of the application, additionally provide a kind of luminescent device being prepared from by above-mentioned manufacture method,
Described luminescent device is electroluminescent device or photo luminescent devices.Due to above-mentioned electroluminescent device and/or above-mentioned photic
Optical device is prepared from by above-mentioned manufacture method, and this manufacture method is by the mask plate by having multiple hollow-out parts
It is arranged on substrate, then uses solwution method to make ink be arranged at the surface of substrate by hollow-out parts, then by the ink of substrate surface
Water is dried, and forms luminescent layer or functional layer, thus utilizes mask plate to block the ink dispersion to other color regions, effectively
Avoid the generation of colour mixture problem, improve the color of the luminescent device with electroluminescent device and/or photo luminescent devices
Degree of accuracy.
According to another aspect of the application, additionally providing a kind of mixed luminescence device, this mixed luminescence device includes electricity
Electroluminescence device and be arranged at the photo luminescent devices of electroluminescent device light emission side, electroluminescent device and/or photic
The manufacture method that optical device is above-mentioned is prepared from.Due to the electroluminescent device in above-mentioned mixed luminescence device and/or photic
Luminescent device is to be prepared from by the manufacture method of above-mentioned luminescent device, and this manufacture method is by having multiple hollow out
The mask plate in portion is arranged on substrate, then uses solwution method to make ink be arranged at the surface of substrate by hollow-out parts, then by base
The ink dried on plate surface, forms luminescent layer or functional layer, thus utilizes mask plate to block ink to other color regions
Dispersion, efficiently avoid the generation of colour mixture problem, improves the mixing with electroluminescent device and/or photo luminescent devices
The color accuracy of luminescent device.
Luminescent device of present invention offer and preparation method thereof is be provided below in conjunction with embodiment.
Embodiment 1
The step of the manufacture method of the mask plate with surface modification that the present embodiment provides includes:
Step S01, immerses in the solution with hydrophobic material by the mask plate being prepared from by nickel alloy, above-mentioned hydrophobic
Property material is 17 fluorine decyl trimethoxy silanes, so that hydrophobic material is fixed on the surface of mask plate;
Step S02, will be fixed with mask plate and the solution separating of hydrophobic material, and be dried by mask plate, be had
Hydrophobic surface modification mask plate.
Embodiment 2
The step of the manufacture method that the surface that the present embodiment provides has the substrate of hydrophilic region and hydrophobic region includes:
Coupling agent and initiator are mixed in a solvent, forms processing substrate liquid, a side surface of transparent substrates is placed
In processing substrate liquid, coupling agent bonding is made to be fixed on the surface of transparent substrates and form bonding surface, by former for the first reaction
Material is arranged on bonding surface, hides the first reaction raw materials being positioned at first area, and is pointed to the first reaction of second area
Raw material carries out ultra-vioket radiation, so that the first reaction raw materials and coupling agent carry out graft reaction under ultra-vioket radiation, thus is formed and dredges
Aqua region, removes the first reaction raw materials of first area, arranges the second reaction raw materials on first area and the second masked areas,
Hide the second reaction raw materials being positioned at the second masked areas, and the second reaction raw materials being pointed to first area carries out ultraviolet photograph
Penetrate, so that the second reaction raw materials and coupling agent carry out graft reaction under ultra-vioket radiation, thus form hydrophilic region, and then obtain
Surface-modified base plate;
Wherein, transparent substrates is glass, and coupling agent is chlorine (dimethyl) vinyl silanes, and initiator is 4-dimethyl pyrazole
Pyridine, the first reaction raw materials 1H, 1H, 2H, 2H-perfluor decyl mercaptan, the second reaction raw materials mercaptoethylmaine, hydrophobic second area pair
Answer the microarray pattern of two group 96 × 64.
Embodiment 3
The manufacture method of the electroluminescent device that the present embodiment provides comprises the following steps:
Step S1, it is provided that have the first electrode base board of pixel isolation structure, pixel isolation structure has 96 × 64 phases
The subpixel area of isolation mutually, the first electrode base board is the substrate having anode layer, and anode layer is ito anode;
Step S2, by embodiment 1 provide surface modification mask plate be arranged at the first electrode base board have pixel every
From the side of structure, the hollow-out parts of mask plate is corresponding with subpixel area;
Step S3, uses inkjet printing (model is Dimatix Materials Printer DMP-2831) technique to make work
Aqueous solution for the PEDOT:PSS of hole injection layer ink is entered in corresponding subpixel area by hollow-out parts;
Step S4, by the hole injection layer ink dried in subpixel area, forms hole injection layer;
Step S5, performs step S2 to S4 again, in step S2 of above-mentioned repetitive process, use prepared by nickel alloy and
The mask plate become, uses hole transmission layer ink in step S3 of above-mentioned repetitive process, and hole transmission layer ink is poly-(9-
Vinyl) toluene solution of carbazole (PVK), to form hole transmission layer in step s 4;
Step S6, performs step S2 to S4 again, in step S2 of above-mentioned repetitive process, use prepared by nickel alloy and
The mask plate become, uses green quantum dot material ink in step S3 of above-mentioned repetitive process, and quanta point material ink is
The decane solution of CdSe/CdS, to form green quantum dot light-emitting zone in step s 4;
Step S7, performs step S2 to S4 again, in step S2 of above-mentioned repetitive process, use prepared by nickel alloy and
The mask plate become, uses red quantum point material ink in step S3 of above-mentioned repetitive process, and quanta point material ink is
The decane solution of CdSe/ZnS, to form red quantum point light-emitting zone in step s 4;
Step S8, performs step S2 to S4 again, in step S2 of above-mentioned repetitive process, uses in embodiment 1 and provides
Surface modification mask plate, step S3 of above-mentioned repetitive process uses electron transfer layer ink and electron injecting layer ink,
And electron transfer layer ink and electron injecting layer ink are the butanol solution of ZnO, to form electric transmission and note in step s 4
Enter layer;
Step S9, is deposited with the second electrode in the side away from the first electrode base board of electron injecting layer, forms cathode layer
Material is Ag.
Embodiment 4
The manufacture method that the present embodiment provides is with the difference of embodiment 3:
It is respectively adopted ultrasonic spraying and makes electric transmission and implanted layer ink, quanta point material ink, hole transmission layer ink
Respectively enteing in subpixel area with hole injection layer ink, the supersonic frequency in above-mentioned ultrasonic spraying coating process is 120kHz.
Embodiment 5
The manufacture method that the present embodiment provides is with the difference of embodiment 4:
Supersonic frequency in ultrasonic spraying coating process is 180kHz.
Embodiment 6
The manufacture method that the present embodiment provides is with the difference of embodiment 4:
Supersonic frequency in ultrasonic spraying coating process is 45kHz.
Embodiment 7
The manufacture method that the present embodiment provides is with the difference of embodiment 4:
Supersonic frequency in ultrasonic spraying coating process is 90kHz.
Embodiment 8
The manufacture method of the photo luminescent devices that the present embodiment provides comprises the following steps:
Step S1, is arranged at the mask plate being prepared from by nickel alloy in embodiment 2 on the surface of surface-modified base plate,
96 × 64 hollow-out parts of mask plate are corresponding with 96 × 64 microarray patterns of one of which of hydrophobic region;
Step S2, uses inkjet printing (model is Dimatix Materials Printer DMP-2831) technique to make to dredge
The red quantum point ink of aqueous is entered in hydrophobic region by hollow-out parts;
Step S3, by the quantum dot ink dried in hydrophobic region;
Step S4, is arranged at aforementioned mask plate on the surface of above-mentioned surface modification mask plate, 96 × 64 of mask plate
Hollow-out parts is corresponding with another 96 × 64 microarray patterns of group of hydrophobic region;
Step S5, uses inkjet printing (model is Dimatix Materials Printer DMP-2831) technique to make to dredge
The green quantum dot ink of aqueous is entered in hydrophobic region by hollow-out parts;
Step S3, by the quantum dot ink dried in hydrophobic region,
Wherein, the viscosity of red and green quantum dot ink is 15cps, and red quantum point material is CdSe/ZnS, green
Color quanta point material is CdSe/CdS, and the hydrophobic ligand of surface both is all oleic acid.
Embodiment 9
The manufacture method that the present embodiment provides is with the difference of embodiment 8:
Redness and the viscosity of green quantum dot ink that inkjet printing uses are 5cps.
Embodiment 10
The manufacture method that the present embodiment provides is with the difference of embodiment 8:
Use ultrasonic spraying to make hydrophobic red quantum point ink and green quantum dot ink be entered by hollow-out parts to dredge
In aqua region, the supersonic frequency in above-mentioned ultrasonic spraying coating process is 120kHz.
Comparative example 1
The step of the manufacture method of the electroluminescent device that this comparative example provides includes:
Step S1, it is provided that have the first electrode base board of pixel isolation structure, pixel isolation structure has 96 × 64 phases
The subpixel area of isolation mutually, the first electrode base board is the substrate having anode layer;
Step S2, uses inkjet printing (model is Dimatix Materials Printer DMP-2831) to make hole note
Enter layer ink to enter in subpixel area;
Step S3, by the hole injection layer ink dried in subpixel area, forms hole injection layer;
Step S4, repeat step S2 to S3, be respectively adopted in step S3 of above-mentioned repetitive process hole transmission layer ink,
Quanta point material ink, electron transfer layer ink, to sequentially form hole transmission layer, luminescent layer, electric transmission in step s 4
Layer;
Step S6, arranges the second electrode in the side away from the first electrode base board of electron transfer layer,
Wherein, electron injecting layer ink, electron transfer layer ink, quanta point material ink, hole transmission layer ink and sky
Cave implanted layer ink is same as in Example 3.
Comparative example 2
The step of the manufacture method of the photo luminescent devices that this comparative example provides includes:
Step S1, coats photoresist on the first surface of transparent substrates, is exposed the most successively and develops, to be formed
Pixel isolation structure, pixel isolation structure has two groups of 96 × 64 mutually isolated subpixel area, and pixel isolation structure
Exposed surface be hydrophilic surface, the adjacent wall isolating matrix in pixel isolation structure is vertical with substrate, adjacent sidewall
Between isolation matrix be isolating bar, and the side surface away from substrate of isolating bar is plane;
Step S1, spin coating red quantum point material on the transparent substrates having pixel isolation structure, then red to being provided with
The transparent substrates of color quanta point material carries out baking process, exposure-processed, development treatment and dried successively, obtains 96 × 64
Individual red quantum lattice array;
Step S2, spin coating green quanta point material on aforesaid substrate, then to being provided with the saturating of green quanta point material
Photopolymer substrate carries out baking process, exposure-processed, development treatment and dried successively, obtains 96 × 64 green quantum dot array
Row,
Wherein, transparent substrates is glass, and the material forming above-mentioned exposed surface is polyimides, red quantum point material ink
Water includes that CdSe/ZnS, green quanta point material include that CdSe/CdS, the viscosity of quanta point material ink are 15cps.
Electroluminescent device in above-described embodiment 3 to 7 and comparative example 1 carries out energising experiment, and control circuit only allows redness
Sub-pixel or green sub-pixels are the most luminous, and with spectrum scan-type luminance meter (PR670) on electroluminescent device uniformly
Choosing each two positions to test its chromaticity coordinates, test result is as shown in table 1.
Table 1
By above-mentioned test result it is apparent that above-described embodiment 3 to 7 uses normal inkjet print and mask plate
In conjunction with or the electroluminescent device that obtains of the processing technology that is combined with mask plate of ultrasonic spraying, the concordance of chromaticity coordinates is preferable;And
The electroluminescent device that the processing technology printed only with normal inkjet in above-mentioned comparative example 1 obtains, the change of chromaticity coordinates is very
Greatly, and from the value of chromaticity coordinates, can be seen that obvious mixed color phenomenon.
Further, after respectively the photo luminescent devices in above-described embodiment 8 to 10 and comparative example 2 being applied seal protection layer,
Being arranged at the light emission side of blue electroluminescent devices (BOLED), control circuit only allows red sub-pixel or green sub-pixels phase
Corresponding Blue backlight is the most luminous, under the exciting of blue light, and corresponding red quantum point or green quantum dot luminescence generated by light,
Uniformly choosing two positions on exiting surface with spectrum scan-type luminance meter (PR670) and test its chromaticity coordinates, test result is such as
Shown in table 2.
Table 2
Embodiment | R1 (x, y) | R2 (x, y) | G1 (x, y) | G2 (x, y) |
Embodiment 8 | 0.6755,0.3219 | 0.6752,0.3225 | 0.1898,0.7454 | 0.1878,0.7424 |
Embodiment 9 | 0.6751,0.3220 | 0.6751,0.3225 | 0.1870,0.7473 | 0.1904,0.7427 |
Embodiment 10 | 0.6745,0.3222 | 0.6755,0.3214 | 0.1941,0.7429 | 0.1936,0.7425 |
Comparative example 2 | 0.6748,0.3225 | 0.6754,0.3230 | 0.1895,0.7447 | 0.1889,0.7456 |
By above-mentioned test result it is apparent that use normal inkjet print be combined with mask plate or ultrasonic spraying and
The photo luminescent devices that the processing technology that mask plate combines obtains, the concordance of chromaticity coordinates is preferable, utilizes in above-mentioned comparative example 2
The photo luminescent devices that conventional exposure imaging prepares is suitable, but reduces the cost of preparation.
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect:
1, the technical scheme using mask plate to be combined with solwution method forms luminescent layer or functional layer, utilizes mask plate to block
Ink, to the dispersion of other color regions, efficiently avoid the generation of colour mixture problem, and the color that improve luminescent device is accurate
Degree;
2, by pixel isolation structure and mask plate being combined, the spraying coating process system in solwution method can not only be utilized
Make pixel, additionally it is possible to utilize the relatively low ink jet printing device of precision to make pixel, thus reduce the accurate inkjet printing of employing
Cost needed for equipment;
3, utilize the mask plate with modified surface that the ink with different hydrophilic and hydrophobic can be made accurately to enter into right
In the subpixel area answered, and pixel isolation structure is utilized to prevent the interregional ink blending of different subpixel, due to mask plate
It is disposed on what pixel isolation structure upper end used, when making large area panel, owing to there being pixel isolation structure around hollow-out parts
Support and be difficult to deformation, thus in efficiently solving different subpixel region, ink injection rate is different or injects deviation and makes
The aberration become or other performance issues;
4, multiple being separated is formed by the hydrophilic region on transparent substrates and hydrophobic region on the surface of transparent substrates
Subpixel area, make hydrophilic quantum dot ink enter hydrophilic region, hydrophobic region is as isolation structure, or makes hydrophobic
Quantum dot ink enters hydrophobic region, and hydrophilic region is as isolation structure, thus it is interregional to effectively prevent different subpixel
Quantum dot ink blending, and then also efficiently solve quantum dot ink blending in different subpixel region and reduce color essence
The problem of parasexuality;
5, comparing the manufacture method arranging pixel isolation structure on the transparent substrate, the above-mentioned manufacture method of the application is not only
Subpixel area needed for can similarly making ink inject, also reduces the cost of manufacture of quantum dot film simultaneously.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, that is made any repaiies
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (12)
1. the manufacture method of a luminescent device, it is characterised in that comprise the following steps:
Step S1, is arranged at the mask plate with multiple hollow-out parts on substrate;
Step S2, uses solwution method to make ink be arranged at the surface of described substrate by described hollow-out parts;
Step S3, by the described ink dried of described substrate surface, forms luminescent layer or functional layer.
Manufacture method the most according to claim 1, it is characterised in that described ink is quanta point material ink, described system
Make method and also include at least being repeated once the process of described step S1 to S3, in each repetitive process, the mask plate used
The zones of different of the corresponding described substrate of hollow-out parts, the glow color of the ink used is the most different.
Manufacture method the most according to claim 1 and 2, it is characterised in that
Described mask plate in described step S1 has modified surface, described modified surface include described mask plate away from described
One side surface of substrate, described modified surface has hydrophilic or hydrophobicity;
The described ink that described step S2 is used has different hydrophilic and hydrophobic from described modified surface.
Manufacture method the most according to claim 3, it is characterised in that described modified surface also includes leaning on of described mask plate
One side surface of nearly described substrate.
Manufacture method the most according to claim 4, it is characterised in that when described modified surface is hydrophobic surface, described
Manufacture method also includes the process forming described modified surface:
Step S01, immerses mask plate and has in the solution of hydrophobic material so that described hydrophobic material be fixed on described in cover
The surface of template, the most described hydrophobic material is fluorine-containing silane coupler;
Step S02, will be fixed with the described mask plate of described hydrophobic material and described solution separating, and enters described mask plate
Row dried, has hydrophobic described modified surface to be formed.
Manufacture method the most according to claim 1 and 2, it is characterised in that described manufacture method also includes described mask
Plate carries out the process of pretreatment, and the process of described pretreatment includes:
The surface of described mask plate is carried out ultraviolet and ozone photodissociation oxidation, so that the hydrophilic surface of described mask plate is the most naked
Dew.
Manufacture method the most according to claim 1 and 2, it is characterised in that
Described substrate in described step S1 has pixel isolation structure, and described pixel isolation structure has multiple mutually isolated
Subpixel area, the corresponding each described subpixel area of described hollow-out parts is arranged;
Described step S2 makes described ink be entered in corresponding described subpixel area by described hollow-out parts.
Manufacture method the most according to claim 1 and 2, it is characterised in that
The surface of the described substrate in described step S1 has hydrophilic region and hydrophobic region, and described hollow-out parts is corresponding described hydrophilic
Region or described hydrophobic region are arranged;
Described step S2 makes hydrophobic described ink be entered in described hydrophobic region by described hollow-out parts, or makes hydrophilic
Described ink is entered in described hydrophilic region by described hollow-out parts.
Manufacture method the most according to claim 1 and 2, it is characterised in that
Described ink is hole-injecting material ink, hole mobile material ink, electron injection material ink and electron transfer layer
Any one in material ink, in described step S3, by described ink dried, to form the hole injection layer of correspondence, hole
Transport layer, electron injecting layer or electron transfer layer;Or
Described ink is quanta point material ink or luminous organic material ink, in described step S3, by described ink dried,
To form corresponding quantum dot light emitting layer or organic luminous layer.
Manufacture method the most according to claim 1 and 2, it is characterised in that use spraying coating process or spray in described step S2
Ink printing technique is so that described ink is arranged at the surface of described substrate by described hollow-out parts, and described spraying coating process is preferably super
Sound sprays.
11. 1 kinds of luminescent devices, it is characterised in that described luminescent device is by making side according to any one of claim 1 to 10
Method is prepared from, and described luminescent device is electroluminescent device or photo luminescent devices.
12. 1 kinds of mixed luminescence devices, described luminescent device includes electroluminescent device and is arranged at described electroluminescent cell
The photo luminescent devices of part light emission side, it is characterised in that described electroluminescent device and/or photo luminescent devices are claim
According to any one of 1 to 10, manufacture method is prepared from.
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US16/328,290 US10943781B2 (en) | 2016-08-26 | 2017-08-24 | Manufacturing method for light emitting device, light emitting device, and hybrid light emitting device |
PCT/CN2017/098811 WO2018036542A1 (en) | 2016-08-26 | 2017-08-24 | Manufacturing method for light emitting device, light emitting device, and hybrid light emitting device |
JP2019531517A JP2019525446A (en) | 2016-08-26 | 2017-08-24 | Light emitting device manufacturing method, light emitting device, and hybrid light emitting device |
KR1020197007403A KR102387760B1 (en) | 2016-08-26 | 2017-08-24 | Manufacturing method of light emitting device, light emitting device and hybrid light emitting device |
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