CN106990464A - Quantum dot color filter and preparation method, liquid crystal panel, liquid crystal display - Google Patents
Quantum dot color filter and preparation method, liquid crystal panel, liquid crystal display Download PDFInfo
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- CN106990464A CN106990464A CN201710385906.3A CN201710385906A CN106990464A CN 106990464 A CN106990464 A CN 106990464A CN 201710385906 A CN201710385906 A CN 201710385906A CN 106990464 A CN106990464 A CN 106990464A
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
- G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
Landscapes
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Optical Filters (AREA)
Abstract
The invention provides quantum dot color filter and preparation method, liquid crystal panel, liquid crystal display, belong to field of liquid crystal display, putting forward this method includes：Black matrix" is formed on the transparent substrate；Using InkJet printing processes, red pixel point, green pixel point and blue pixel point are formed respectively in the space of black matrix"；When forming red pixel point and forming green pixel point, it will be mixed for the reaction raw materials for preparing red light quantum point or green light quantum point with light-cured resin system, in the space that black matrix" is injected using InkJet printing processes, under the conditions of ultraviolet light, insulation reaction preset time.This method can make the quantum dot to be formed dispersed, will not be absorbed in the forming process of quantum dot and convert ultraviolet light, have great importance for light extraction efficiency, light conversion efficiency, uniformity and the stability for improving colored filter.
Description
Technical field
The present invention relates to field of liquid crystal display, more particularly to a kind of quantum dot color filter and preparation method, liquid crystal surface
Plate, liquid crystal display.
Background technology
With continuing to develop for lcd technology, consumer requires more and more higher to the colour gamut of liquid crystal display.Mesh
Before, by the way that quantum dot color filter to be arranged on to the polarizer of liquid crystal panel and the side of liquid crystalline phase pair, to improve liquid crystal
Show the colour gamut of equipment.Fig. 1 shows a kind of structure of common quantum dot color filter, including：Transparency carrier 1 and shape
Into the quantum dot light conversion layer 2 on transparency carrier 1.Wherein, quantum dot light conversion layer 2 includes multiple pixels 21 and used
In the black matrix" 22 for separating pixel 21.Pixel 21 includes red pixel point 21a, green pixel point 21b and indigo plant
Colour vegetarian refreshments 21c, they are formed in the space in black matrix" 22 in particular order.
Prior art is prepared via a method which to obtain the quantum dot color filter of said structure：Shape on the transparent substrate
Into black matrix"；Red light quantum point, the light-cured resin system of green light quantum point, mixing are blended with using InkJet printing processes
The light-cured resin system for having scattering particles is filled into the space of black matrix", after ultraviolet light, sequentially forms red
Pixel 21a, green pixel point 21b, blue pixel point 21c.Wherein, light-cured resin system is the common transparent light in this area
Resin is learned, in order to which light is passed through.
Inventor has found that prior art at least has following technical problem：
On the one hand, quantum dot is poor with light-cured resin Miscibility, and it is difficult dispersed wherein to make quantum dot, and then
Cause inkjet printing controllable and homogeneity is poor；On the other hand, during ultraviolet photoetching, quantum dot can absorb ultraviolet with transform portion
Light, influences the solidification effect of light-cured resin.Both of the above can influence the light extraction efficiency and light of formed colored filter to turn
Change efficiency.
The content of the invention
In order to solve the above-mentioned technical problem, the embodiments of the invention provide a kind of quantum dot color filter and preparation side
Method, liquid crystal panel, liquid crystal display.Concrete technical scheme is as follows：
First aspect there is provided a kind of preparation method of quantum dot color filter, including：Formed on the transparent substrate black
Colour moment battle array；
Using InkJet printing processes, red pixel point, green pixel point are formed respectively in the space of the black matrix"
With blue pixel point；
When forming the red pixel point and forming the green pixel point, it will be used to prepare red light quantum point or green
The reaction raw materials of light quanta point are mixed with light-cured resin system, and the space of the black matrix" is injected using InkJet printing processes
In, under the conditions of ultraviolet light, insulation reaction preset time.
Alternatively, the preparation method includes：
It will mix, noted using InkJet printing processes with light-cured resin system for the reaction raw materials for preparing red light quantum point
In the first space for entering the black matrix", under the conditions of ultraviolet light, the preset time of insulation reaction first forms red picture
Vegetarian refreshments；
It will mix, noted using InkJet printing processes with light-cured resin system for the reaction raw materials for preparing green light quantum point
In the Second gap for entering the black matrix", under the conditions of ultraviolet light, the preset time of insulation reaction second forms green picture
Vegetarian refreshments；
Using InkJet printing processes, the black matrix" will be injected for the light-cured resin system for preparing blue pixel point
The 3rd space in, carry out ultraviolet light, formed blue pixel point.
Specifically, preferably, the CdSe that it is 8-10nm that the red light quantum point, which is granularity,；
The green light quantum point is the CdSe that granularity is 3-5nm；
First preset time is 20-30s；
Second preset time is 10-15s.
Specifically, preferably, described include for preparing red light quantum point and the reaction raw materials of green light quantum point：Before Cd
Liquid solution and Se precursor solutions；
The Cd precursor solutions are：Mass ratio is 1:2-5 cadmium oleate：Octadecylene；
The Se precursor solutions are：Mass ratio is 1:5:5 selenium：Tributyl phosphate：Octadecylene, or H2Se aqueous phase is molten
Liquid.
Alternatively, when the Se precursor solutions are：Mass ratio is 1:5:5 selenium：Tributyl phosphate：It is described during octadecylene
Red pixel point or the formation green pixel point are formed, including：
The Cd precursor solutions are well mixed with the light-cured resin system, and are injected into using InkJet printing processes
In first space or the Second gap, 80-110 DEG C is heated under inert atmosphere protection；
Continue to inject the Se precursor solutions into first space or the Second gap using InkJet printing processes,
Under the conditions of ultraviolet light, be heated to 240-280 DEG C and the first preset time described in insulation reaction or it is described second it is default when
Between, form the red pixel point or green pixel point.
Alternatively, when the Se precursor solutions are：H2During Se aqueous phase solution, the formation red pixel point or the shape
Into green pixel point, including：
The Cd precursor solutions are well mixed with the light-cured resin system, are placed in aqueous phase solvent, emulsification is added
Agent, microemulsion is formed under the emulsifying rate more than 15000r/min；
The microemulsion is well mixed with the Se precursor solutions, emulsified feedstock liquid is formed；
The emulsified feedstock liquid is injected into first space or the Second gap using InkJet printing processes, so
Afterwards, continue to inject demulsifier into first space or the Second gap using InkJet printing processes, after being demulsified, in purple
Under the conditions of outer light irradiation, 240-280 DEG C and the first preset time described in insulation reaction or second preset time, shape are heated to
Into the red pixel point or green pixel point.
Specifically, the formation blue pixel point, including：
Scattering particles is mixed with light-cured resin system, the 3rd space is injected into using InkJet printing processes, is passed through
Ultraviolet light, forms the blue pixel point.
Specifically, preferably, described form black matrix" on the transparent substrate, including：
One layer of Cr metal level is deposited on the transparent substrate；
Using photoetching process the black matrix" is formed on the Cr metal levels.
Second aspect is prepared there is provided a kind of quantum dot color filter by above-mentioned preparation method.
There is provided a kind of liquid crystal panel, including above-mentioned quantum dot color filter for the third aspect.
There is provided a kind of liquid crystal display, including above-mentioned liquid crystal panel for fourth aspect.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
The embodiment of the present invention is by making the preparing raw material of quantum dot directly be mixed with light-cured resin system, and in-situ preparation
Quantum dot, on the one hand, the quantum dot to be formed can be made dispersed wherein, makes inkjet printing homogeneous controllable；On the other hand, measure
It will not be absorbed in the forming process of son point and convert ultraviolet light, and then not interfere with the solidification effect of light-cured resin system, it is right
Have great importance in light extraction efficiency, light conversion efficiency, uniformity and the stability for improving colored filter.
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, makes required in being described below to embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For those of ordinary skill in the art, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the structural representation for the quantum dot color filter that prior art is provided；
Fig. 2-1 is provided according to an exemplary embodiment, forms view during red pixel point；
Fig. 2-2 is provided according to an exemplary embodiment, after after the formation of red pixel point, when forming green pixel point
View；
Fig. 3 is the structural representation of the quantum dot color filter provided according to an exemplary embodiment；
Fig. 4 is the structural representation of the liquid crystal panel provided according to an exemplary embodiment.
Reference is：
100- quantum dot color filters；
1- transparency carriers；
2- quantum dot light conversion layers；
21- pixels；
21a- red pixels point, 21b- green pixels point, 21c- blue pixels point；
22- black matrix"s；
3- protective layers；
200- backlight modules；
300- glass substrates；
Polarizer under 400-；
500- liquid crystal modules；
600- upper polarizers.
Embodiment
Unless otherwise defined, all technical terms used in the embodiment of the present invention are respectively provided with usual with those skilled in the art
The identical implication of understanding.To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to this hair
Bright embodiment is described in further detail.
In a first aspect, the embodiments of the invention provide a kind of preparation method of quantum dot color filter, the preparation method
Including：Black matrix" is formed on the transparent substrate；
Using InkJet printing processes, red pixel point, green pixel point and indigo plant are formed respectively in the space of black matrix"
Colour vegetarian refreshments.
Especially, when forming red pixel point and forming green pixel point, it will be used to prepare red light quantum point or green
The reaction raw materials of light quanta point are mixed with light-cured resin system, in the space that black matrix" is injected using InkJet printing processes,
Under the conditions of ultraviolet light, insulation reaction preset time.
Method provided in an embodiment of the present invention, is forming red pigment pixel and during green pixel point, by by their system
Standby raw material is mixed with light-cured resin system, in the space that respective place is injected into using InkJet printing processes, in ultraviolet lighting
Under the conditions of penetrating, light-cured resin system gradually solidifies, at the same time, and red light quantum point and green light quantum point are in insulation reaction process
In gradually form, i.e., light-cured resin system carry out photocuring while, original position prepares quantum dot.
It can be seen that, the embodiment of the present invention is by making the preparing raw material of quantum dot directly be mixed with light-cured resin system, and original
Position generation quantum dot, on the one hand, the quantum dot to be formed can be made dispersed wherein, make inkjet printing homogeneous controllable；It is another
It will not be absorbed in aspect, the forming process of quantum dot and convert ultraviolet light, and then not interfere with the solidification of light-cured resin system
Effect, has great importance for light extraction efficiency, light conversion efficiency, uniformity and the stability for improving colored filter.
Wherein, red light quantum point is different with the insulation reaction time of green light quantum point, i.e., by controlling insulation reaction to carry out
The different time, pointedly to obtain red light quantum point and green light quantum point.It is each being prepared using InkJet printing processes injection
During the material liquid of pixel, it can specifically be realized using ink-jet printer.
The embodiment of the present invention is not limited the sequencing for forming red pixel point, green pixel point and blue pixel point
It is fixed, it can adjust at any time according to the actual requirements, for example, red pixel point, green pixel point and blue picture can be sequentially formed
Vegetarian refreshments, or, green pixel point, red pixel point and blue pixel point etc. can also be sequentially formed.The shape of above-mentioned each pixel
It is independent progress into process, it will not be influenceed by other pixels, also will not cause any to the formation of other pixels
Influence, to ensure that the forming position of pixel is accurate.
As a kind of example, the embodiments of the invention provide a kind of preparation method of quantum dot color filter, including：According to
Formation red pixel point, formation green pixel point and the formation blue pixel point of secondary progress：
(1) red pixel point is formed, is included again：
It will mix, noted using InkJet printing processes with light-cured resin system for the reaction raw materials for preparing red light quantum point
In the first space for entering the black matrix", under the conditions of ultraviolet light, the preset time of insulation reaction first forms red picture
Vegetarian refreshments.
The preparing raw material of red pixel point is directly injected into first where red pixel point using InkJet printing processes
(referring to Fig. 2-1) in space, it is ensured that red pixel point is precisely formed between black matrix".
(2) green pixel point is formed, is included again：
It will mix, noted using InkJet printing processes with light-cured resin system for the reaction raw materials for preparing green light quantum point
In the Second gap for entering the black matrix", under the conditions of ultraviolet light, the preset time of insulation reaction second forms green picture
Vegetarian refreshments.
Treat after the formation of red pixel point, be directly injected into the preparing raw material of green pixel point using InkJet printing processes
In Second gap where green pixel point (referring to Fig. 2-2), so that it is guaranteed that green pixel point is precisely formed in black matrix"
Between, and red pixel point will not be impacted.
(3) form blue pixel point includes again：
The black matrix" will be injected using InkJet printing processes for the light-cured resin system for preparing blue pixel point
The 3rd space in, carry out ultraviolet light, formed blue pixel point.
It can be seen that, above-mentioned each pixel is prepared using InkJet printing processes, is had the advantages that efficient, accurate, controllable.
As another example, the embodiments of the invention provide the preparation method of another quantum dot color filter, bag
Include：Formation green pixel point, formation red pixel point and the formation blue pixel point carried out successively：
(1) green pixel point is formed, is included again：
It will mix, noted using InkJet printing processes with light-cured resin system for the reaction raw materials for preparing green light quantum point
In the Second gap for entering the black matrix", under the conditions of ultraviolet light, the preset time of insulation reaction second forms green picture
Vegetarian refreshments.
(2) red pixel point is formed, is included again：
It will mix, noted using InkJet printing processes with light-cured resin system for the reaction raw materials for preparing red light quantum point
In the first space for entering the black matrix", under the conditions of ultraviolet light, the preset time of insulation reaction first forms red picture
Vegetarian refreshments.
(3) blue pixel point is formed, is included again：
The black matrix" will be injected using InkJet printing processes for the light-cured resin system for preparing blue pixel point
The 3rd space in, carry out ultraviolet light, formed blue pixel point..
It is similar with above-mentioned preparation method, it is used as another example, quantum dot color filter provided in an embodiment of the present invention
Preparation method, can also include：The green picture of formation blue pixel point, formation red pixel point and formation carried out successively
Vegetarian refreshments.Or, formation blue pixel point, formation green pixel point and the formation red pixel point carried out successively.With reference to
On, the embodiment of the present invention is not described in detail at this to their specific steps.
Red light quantum point is that its emission wavelength is different with the difference of green light quantum point, the excitation wavelength of red light quantum point
For 625-640nm, and a length of 525-535nm of the excitation light wave of green light quantum point.For being prepared using identical preparing raw material
Red light quantum point and green light quantum point for, by controlling their granule size to realize the control to its excitation wavelength
System, and their granule size can be determined by controlling their reaction to generate time or other operating parameters.
For example, when they are CdSe quantum dot, the granularity of red light quantum point is made for 8-10nm, such as 8nm,
8.5nm, 9nm, 9.5nm, 10nm etc., with a length of 625-640nm of the excitation light wave for ensuring red light quantum point；Make green light quantum point
Granularity is 3-5nm, such as 3nm, 3.5nm, 4nm, 4.5nm, 5nm, with a length of 525- of the excitation light wave for ensuring green light quantum point
535nm。
The method provided based on the embodiment of the present invention, by controlling the preset time difference of insulation reaction to obtain difference
The quantum dot of granularity, for red light quantum point, control insulation reaction time, i.e. the first preset time are 20-30s, for example
20s, 23s, 25s, 27s, 29s, 30s etc.；For green light quantum point, when controlling its insulation reaction time, i.e., second to preset
Between be 10-15s, such as 10s, 12s, 13s, 14s, 15s.
As a kind of example, when red light quantum point and green light quantum point are CdSe quantum dot, for preparing feux rouges amount
The reaction raw materials of son point and green light quantum point include：Cd precursor solutions and Se precursor solutions；
Cd precursor solutions are：Mass ratio is 1:2-5, such as 1:2、1:3、1:4、1:The cadmium oleate of 5 grades：Octadecylene；
Se precursor solutions are：Mass ratio is 1:5:5 selenium：Tributyl phosphate：Octadecylene, or Se precursor solutions are：
H2Se aqueous phase solution.
Wherein, it is to increase the dispersiveness of Cd precursors, i.e. cadmium oleate using the purpose of octadecylene in Cd precursor solutions.
In Se precursor solutions, by using the tributyl phosphate and octadecylene of said ratio, they are used as synthesis quantum dot
Non-coordinating solvent, dispersing uniformity of the formed quantum dot in light-cured resin can be effectively improved.Or, using H2Se's
Aqueous phase solution, can equally reach the purpose for the dispersing uniformity for effectively improving quantum dot in light-cured resin.
Specifically, above-mentioned Cd precursor solutions are prepared by method as described below：
First, cadmium oleate is prepared：It is 1 by mol ratio in argon gas atmosphere:4 cadmium oxide (CdO) is mixed with oleic acid, so
After be heated to 80 DEG C -120 DEG C (such as 100 DEG C) and keep 20-30mim afterwards, to reduce the viscosity of oleic acid, improve its mobility, plus
Fast dissolution velocity of the cadmium oxide in oleic acid is easy to both sufficiently uniformly to mix.Then, 200-250 DEG C is being heated to, for example
220 DEG C of reaction a period of times, until cadmium oleate is formed completely, it is cooled to room temperature stand-by.
Secondly, in mass ratio, cadmium oleate, octadecylene are uniformly mixed, that is, form Cd precursor solutions.
When Se precursor solutions are：Mass ratio is 1:5:5 selenium：Tributyl phosphate：During octadecylene, pass through side as described below
Method prepares above-mentioned Se precursor solutions：
Under anaerobic, in mass ratio, dissolve selenium in tributyl phosphate and be well mixed, then add octadecylene and enter
Row dilution, you can obtain Se precursor solutions.
After prepared by Cd precursor solutions and Se precursor solutions, use them to prepare quantum dot：
As a kind of example, when Se precursor solutions are：Mass ratio is 1:5:5 selenium：Tributyl phosphate：, should during octadecylene
The forming method of red pixel point or green pixel point includes：
Step 1) Cd precursor solutions are well mixed with light-cured resin system, it is injected into first using InkJet printing processes
In space or Second gap, 80-110 DEG C is heated under inert atmosphere protection.
Step 2) continue to inject Se precursor solutions into the first space or Second gap using InkJet printing processes, ultraviolet
Under the conditions of light irradiation, 240-280 DEG C and the preset time of insulation reaction first or the second preset time are heated to, red pixel is formed
Point or green pixel point.
Wherein, by step 1) viscosity of reactant system is reduced, to ensure that Cd precursors are uniformly distributed therein, simultaneously
It is easy to being sufficiently injected for Se precursor solutions.Wherein, inert atmosphere can use argon gas atmosphere.
By step 2) control the solidification of light-cured resin system, and CdSe quantum dot in-situ preparation.Wherein, lead to
Spend the time of control insulation reaction to control the granularity of CdSe quantum dot, and then realize the control to its excitation wavelength.In addition,
When injecting Se precursor solutions, injection rate is as fast as possible, for example, injection rate can be 20-40ml/min, for example
Can be for 20ml/min, 25ml/min, 30ml/min, 35ml/min etc., preferably 30ml/min, the purpose is to prevent local mistake
React and cause particle diameter to be difficult to control to, beneficial to the size controlling of formed quantum dot, and be beneficial to make the uniform particle sizes of quantum dot.
As another example, when Se precursor solutions are：H2During Se aqueous phase solution, the red pixel point or green pixel
The forming method of point, including：
Step 1*) Cd precursor solutions are well mixed with light-cured resin system, it is placed in aqueous phase solvent, adds emulsification
Agent, microemulsion is formed under the emulsifying rate more than 15000r/min.
Step 2*) microemulsion is well mixed with Se precursor solutions, form emulsified feedstock liquid.
Step 3*) emulsified feedstock liquid is injected into the first space or Second gap using InkJet printing processes, then, profit
Continued to inject demulsifier into the first space or Second gap with InkJet printing processes, after being demulsified, in ultraviolet light condition
Under, 240-280 DEG C and the preset time of insulation reaction first or the second preset time are heated to, red pixel point or green picture is formed
Vegetarian refreshments.
Wherein, by step 1*) come make Cd precursor solutions fully and be evenly dispersed in light-cured resin system.Its
In, the aqueous phase solvent used can be water etc., and effect is easy for Cd precursors being dispersed into microemulsion in the presence of emulsifying agent.
The emulsifying agent used can be cetyl trimethylammonium bromide (CTAB etc.), and it has amphiphilic, inner side oleophylic and outside
It is hydrophilic, the microemulsion for forming Cd precursor solutions can be beneficial under emulsification.Emulsifying rate can for 20000r/min,
25000r/min, 30000r/min, 35000r/min, 40000r/min etc..
It will be appreciated by persons skilled in the art that, the content for aqueous phase solvent and emulsifying agent is not construed as limiting, as long as water
Phase solvent can be realized dispersed, and emulsifying agent can realize enough emulsification.
Step 2*) in, because Se precursor solutions are H2Se aqueous phase solution, by by itself and step 1*) micro emulsion that is formed
Liquid is well mixed, and it as aqueous phase reactions thing, can form the raw material of CdSe quantum dot.
By step 3*) synchronously carry out quantum dot growth and light-cured resin system solidification, wherein, by
Demulsifier is injected in emulsified feedstock liquid, emulsified feedstock liquid is demulsified, to realize that fast reaction forms CdSe quantum dot.It is used
Demulsifier can be acetone etc..
It will be appreciated by persons skilled in the art that the amount to demulsifier is also not construed as limiting, as long as it, which can be realized, makes breast
Change material liquid to be demulsified completely.
When carrying out ultraviolet light, bilateral irradiation is carried out to mixed solution, so that above-mentioned preparation process uniform, controllable.Can
With understanding, red light quantum point is formed in the first space, green light quantum point is formed in Second gap.
After red pixel point and green pixel point is formed, blue pixel point is sequentially re-formed, wherein, in black matrix"
Space in formed blue pixel point, including：
Scattering particles is mixed with light-cured resin system, the 3rd sky of black matrix" is injected into using InkJet printing processes
Gap, through ultraviolet light, forms blue pixel point.
Wherein, scattering particles can be TiO2Particle, PC particles (makrolon particle).In order to obtain good saturating blue light
Effect, the granularity of above-mentioned scattering particles can be 50nm-200nm, such as 50nm, 70nm, 90nm, 120nm, 140nm, 160nm,
180nm, 200nm etc., also, scattering particles and the mass ratio of light-cured resin system can be 1:20-50, such as 1:20、1:
22、1:25、1:28、1:30 etc..
In the embodiment of the present invention, there is no special restriction, this area routine techniques hand for the forming process of black matrix"
Section.For example, the technique formation black matrix" that can be combined by photoetching and etching phase, the material of black matrix" can be gold
Belong to the opaque materials such as chromium (Cr) or phenolic resin.
As a kind of example, black matrix" is formed on the transparent substrate, including：One layer of Cr metal is deposited on the transparent substrate
Layer；Using photoetching process black matrix" is formed on Cr metal levels.
Wherein, transparency carrier can select glass plate, can by liquid phase deposition deposit thickness thereon be 80-120 μ
M Cr metal levels.
, it is necessary to use mask plate to form black matrix pattern mould during using photoetching process formation black matrix"
Plate, it is necessary to remove the Cr metal levels at each pixel position using etching liquid after uv-exposure, development, to be formed
Black matrix" area.
Wherein, etching liquid preferably (NH4)2Ce(NO3)5, often in 100ml etching liquid, ammonium ceric nitrate is 5 grams -20 grams, high
Chloric acid is 1.5 milliliters -8 milliliters, and surplus is water.
It will be appreciated by persons skilled in the art that in above-mentioned preparation method, the photocuring tree for forming each pixel
Resin system includes matrix resin and light trigger, and wherein light trigger quality is the 0.2-4% of light-cured resin system quality, root
Adjusted according to actual demand, the embodiment of the present invention is not especially limited herein.
In the embodiment of the present invention, the matrix resin in light-cured resin system can be unsaturated polyester resin, asphalt mixtures modified by epoxy resin
At least one of transparent resin such as fat acrylic resin and mercaptan/vinyl monomer Photopolymer System.
Wherein, Epocryl is specifically as follows bisphenol A epoxy acrylate resin.Those skilled in the art can
With understanding, matrix resin should be transparent resin.In addition, in the matrix resin of light-cured resin, generally also containing poly- first
Base methyl acrylate (PMMA) particle, polymethyl methacrylate particulate is as diffusion particle, to increase the optical filtering of quantum stippling color
The visual angle of piece.
Light trigger can be benzoin class light trigger, benzil class light trigger, Benzophenone-type light initiator, sulphur
Miscellaneous anthrone photoinitiator and fear at least one of ultraviolet initiators such as quinones light trigger, or cyclopentadiene-
The light triggers such as iron.
For example, benzoin class light trigger is specifically as follows：Benzoin, benzoin alkylether etc.；Benzil class light
Initiator is specifically as follows diphenylethan, 2,4,6- trimethylbenzoyls phosphinic acid ethyl ester (TPO-L) etc.；Benzophenone light
Initiator is specifically as follows benzophenone, 2,4 dihydroxyl benzophenone etc.；Thioxanthone photoinitiator is specifically as follows 2-
Isopropyl thioxanthone (ITX) etc.；Fear quinones light trigger and be specifically as follows and fear quinone etc..
In order to simplify the preparation process of quantum dot color filter, it is preferred to use identical matrix resin and light trigger kind
Class and identical proportioning, by changing the ultraviolet light time, to realize to light-cured resin crosslinking degree and be formed
The control of quantum dot granule size.
For example, the combination of following matrix resin and light trigger can be used：
1) matrix resin：Methyl methacrylate (MMA), light trigger：2,4- diethyl thioxanthones (DETX), light draws
It is 2~3% that hair agent consumption, which accounts for MMA and the percentage of light trigger total amount,.
2) matrix resin：Methyl methacrylate (MMA), light trigger：The Irgacure2959 type light of BASF AG
Initiator, it is 2~3% that light trigger consumption, which accounts for MMA and the percentage of light trigger total amount,.
3) matrix resin：Epoxy resin E-51, light trigger：Cyclopentadiene-iron, light trigger consumption account for epoxy resin and
The percentage of light trigger total amount is 3~4%.
The light conversion efficiency of quantum dot in each pixel due to different colours is different, therefore its content is also different, such as
The luminous efficiency and white field color dot of this influence quantum dot color filter, are adjusted according to the actual requirements.In order to ensure
Higher luminous efficiency, while white field color dot is in (0.280,0.290) CIE1931, the quality for typically making quantum dot is photocuring
The 1-5% of resin system quality, preferably 3-5%.For example, for red light quantum point, its quality is preferably photocuring
The 3-5% of resin system quality, and for green light quantum point, in order to reach effect same, its quality is red light quantum point
1.1-1.2 times of quality.
In the preparation method of quantum dot color filter provided in an embodiment of the present invention, prepared in quantum dot light conversion layer
Bi Hou, is additionally included on quantum dot light conversion layer and forms protective layer, for example silica water oxygen barrier layer.The silica water
Oxygen barrier layer can be using chemical gaseous phase depositing process formation on quantum dot light conversion layer.
Second aspect, the embodiments of the invention provide a kind of quantum dot color filter, the quantum dot color filter by
Above-mentioned preparation method is prepared.
Fig. 3 shows a kind of structure of quantum dot color filter, including transparency carrier 1, formation are on transparency carrier 1
Quantum dot light conversion layer 2, form protective layer 3 on quantum dot light conversion layer 2, wherein, quantum dot light conversion layer 2 includes
Multiple pixels 21 and the black matrix" 22 for pixel 21 to be separated.Pixel 21 includes red pixel point 21a, green
Colour vegetarian refreshments 21b and blue pixel point 21c.
According to described above, the quantum dot color filter is prepared by the above method, and light efficiency is gone out with excellent
Rate, light conversion efficiency, uniformity and stability.
The third aspect, the embodiments of the invention provide a kind of liquid crystal panel, the liquid crystal panel includes above-mentioned quantum stippling
Colo(u)r filter.
According to described above, due to the quantum dot color filter used in liquid crystal panel have excellent light extraction efficiency,
Light conversion efficiency, uniformity and stability, therefore, liquid crystal panel provided in an embodiment of the present invention have excellent display effect.
Fig. 4 shows a kind of structural representation of liquid crystal panel, and it includes the backlight module being sequentially formed from bottom to top
200th, glass substrate 300, lower polarizer 400, liquid crystal module 500, upper polarizer 600 and quantum dot color filter 100.
Fourth aspect, the embodiments of the invention provide a kind of liquid crystal display, the liquid crystal display includes above-mentioned
Liquid crystal panel.
Quantum dot color filter provided in an embodiment of the present invention can be covered on above the upper polarizer of liquid crystal panel, energy
The liquid crystal display is enough set to realize that high colour gamut high efficiency is shown.
Liquid crystal display described in the embodiment of the present invention is specifically as follows LCD TV, notebook computer screen, put down
Any product or part with display function such as plate computer, mobile phone.
Technical scheme is described in detail below by specific embodiment.In the examples below,
Prepared red light quantum point and green light quantum point is CdSe quantum dot, for preparing red light quantum point and green glow
The reaction raw materials of quantum dot include：Cd precursor solutions and Se precursor solutions.
Wherein, Cd precursor solutions are：Mass ratio is 1:5 cadmium oleate：Octadecylene.
Se precursor solutions used in embodiment 1-3 are：Mass ratio is 1:5:5 selenium：Tributyl phosphate：Octadecylene.
Se precursor solutions used in embodiment 4-6 are：H2Se aqueous phase solution.
In used light-cured resin system, matrix resin is methyl methacrylate (MMA), light trigger：2,4-
Diethyl thioxanthone (DETX), it is 3% that light trigger consumption, which accounts for MMA and the percentage of light trigger total amount,.
The quality of formed red light quantum point is the 4% of light-cured resin system quality, forms the matter of green light quantum point
Measure as the 4.5% of light-cured resin system quality, the mass ratio between each raw material can be obtained accordingly.
Raw materials used unreceipted production firm and specification person are can be by the conventional products of acquisition purchased in market.
Embodiment 1
The present embodiment provides a kind of quantum dot color filter and preparation method thereof, the structure of the quantum dot color filter
As shown in figure 3, including transparency carrier 1, the quantum dot light conversion layer 2 formed on transparency carrier 1, being formed in quantum dot light turn
The protective layer 3 changed on layer 2, wherein, quantum dot light conversion layer 2 includes multiple pixels 21 and for pixel 21 to be separated
The black matrix" 22 opened.Pixel 21 includes red pixel point 21a, green pixel point 21b and blue pixel point 21c.
The preparation method of the quantum dot color filter comprises the following steps：
Step 101, black matrix" is formed on the transparent substrate, be specially：
Deposition a layer thickness is 100 μm of Cr metal levels on the transparent substrate, using photoetching process on Cr metal levels shape
Into black matrix".(NH is selected in photoetching process4)2Ce(NO3)5Etching liquid.
Step 102, formation red pixel point, be specially：
Cd precursor solutions are well mixed with light-cured resin system, and the first space is injected into using InkJet printing processes
It is interior, 100 DEG C are heated under inert atmosphere protection；
With 30ml/min speed, continue to inject Se precursor solutions into the first space using InkJet printing processes, in ripple
Long 350nm, power 900mw/m2Ultraviolet light under the conditions of, be heated to 260 DEG C and insulation reaction 20s, form red pixel
Point.
Step 103, formation green pixel point, include again：
Cd precursor solutions are well mixed with light-cured resin system, and Second gap is injected into using InkJet printing processes
It is interior, 100 DEG C are heated under inert atmosphere protection；
With 30ml/min speed, continue to inject Se precursor solutions into Second gap using InkJet printing processes, in ripple
Long 350nm, power 900mw/m2Ultraviolet light under the conditions of, be heated to 260 DEG C and insulation reaction 10s, form green pixel
Point.
Step 104, formation blue pixel point, include again：
It is 1 by mass ratio:25 TiO2The mixing material of particle and light-cured resin system is filled in the 3rd space, profit
With wavelength 350nm, power 900mw/m2Ultraviolet light, formed blue pixel point.
Step 105, after quantum dot light conversion layer prepare finish after, using chemical vapour deposition technique in quantum dot light conversion layer
On deposit layer of silicon dioxide water oxygen barrier layer.
After tested, the excitation wavelength of prepared red pixel point is between 625-630nm, and green pixel point is excited
Optical wavelength is between 525-528nm.
Embodiment 2
The present embodiment is identical with the preparing raw material and operating procedure of embodiment 1, and difference is, is forming red pixel point
When, the insulation reaction time is 25s；When forming green pixel point, the insulation reaction time is 12s.
After tested, the excitation wavelength of prepared red pixel point is between 630-635nm, and green pixel point is excited
Optical wavelength is between 528-531nm.
Embodiment 3
The present embodiment is identical with the preparing raw material and operating procedure of embodiment 1, and difference is, is forming red pixel point
When, the insulation reaction time is 30s；When forming green pixel point, the insulation reaction time is 15s.
After tested, the excitation wavelength of prepared red pixel point is between 635-640nm, and green pixel point is excited
Optical wavelength is between 531-535nm.
Embodiment 4
The present embodiment provides a kind of quantum dot color filter and preparation method thereof, the structure of the quantum dot color filter
As shown in figure 3, including transparency carrier 1, the quantum dot light conversion layer 2 formed on transparency carrier 1, being formed in quantum dot light turn
The protective layer 3 changed on layer 2, wherein, quantum dot light conversion layer 2 includes multiple pixels 21 and for pixel 21 to be separated
The black matrix" 22 opened.Pixel 21 includes red pixel point 21a, green pixel point 21b and blue pixel point 21c.
The preparation method of the quantum dot color filter comprises the following steps：
Step 101, black matrix" is formed on the transparent substrate, be specially：
Deposition a layer thickness is 100 μm of Cr metal levels on the transparent substrate, using photoetching process on Cr metal levels shape
Into black matrix".(NH is selected in photoetching process4)2Ce(NO3)5Etching liquid.
Step 102, formation red pixel point, be specially：
Cd precursor solutions are well mixed with light-cured resin system, are subsequently placed in water, emulsifying agent cetyl is added
Trimethylammonium bromide, microemulsion is formed under 25000r/min emulsifying rate.
The microemulsion is well mixed with Se precursor solutions, emulsified feedstock liquid is formed.
The emulsified feedstock liquid is injected into the first space using InkJet printing processes, then, InkJet printing processes are utilized
Continue to inject demulsifier acetone into the first space, after being demulsified, in wavelength 350nm, power 900mw/m2Ultraviolet light
Under the conditions of, 260 DEG C and insulation reaction 20s are heated to, red pixel point is formed.
Step 103, formation green pixel point, include again：
Cd precursor solutions are well mixed with light-cured resin system, are subsequently placed in water, emulsifying agent cetyl is added
Trimethylammonium bromide, microemulsion is formed under 25000r/min emulsifying rate.
The microemulsion is well mixed with Se precursor solutions, emulsified feedstock liquid is formed.
The emulsified feedstock liquid is injected into Second gap using InkJet printing processes, then, InkJet printing processes are utilized
Continue to inject demulsifier acetone into Second gap, after being demulsified, in wavelength 350nm, power 900mw/m2Ultraviolet light
Under the conditions of, 260 DEG C and insulation reaction 10s are heated to, red pixel point is formed.
Step 104, formation blue pixel point, include again：
Using InkJet printing processes, will be mixed with mass fraction is 1:25 TiO2The light-cured resin system injection the of particle
In three spaces, wavelength 350nm, power 900mw/m are utilized2Ultraviolet light, formed blue pixel point.
Step 105, after quantum dot light conversion layer prepare finish after, using chemical vapour deposition technique in quantum dot light conversion layer
On deposit layer of silicon dioxide water oxygen barrier layer.
After tested, the excitation wavelength of prepared red pixel point is between 625-630nm, and green pixel point is excited
Optical wavelength is between 525-528nm.
Embodiment 5
The present embodiment is identical with the preparing raw material and operating procedure of embodiment 4, and difference is, is forming red pixel point
When, the insulation reaction time is 25s；When forming green pixel point, the insulation reaction time is 12s.
After tested, the excitation wavelength of prepared red pixel point is between 630-635nm, and green pixel point is excited
Optical wavelength is between 528-531nm.
Embodiment 6
The present embodiment is identical with the preparing raw material and operating procedure of embodiment 4, and difference is, is forming red pixel point
When, the insulation reaction time is 30s；When forming green pixel point, the insulation reaction time is 15s.
After tested, the excitation wavelength of prepared red pixel point is between 635-640nm, and green pixel point is excited
Optical wavelength is between 531-535nm.
Presently preferred embodiments of the present invention is the foregoing is only, the protection domain being not intended to limit the invention is all in this hair
Within bright spirit and principle, any modification, equivalent substitution and improvements made etc. should be included in protection scope of the present invention
Within.
Claims (11)
1. a kind of preparation method of quantum dot color filter, including：Black matrix" is formed on the transparent substrate；
Using InkJet printing processes, red pixel point, green pixel point and indigo plant are formed respectively in the space of the black matrix"
Colour vegetarian refreshments；
Characterized in that, when forming the red pixel point and forming the green pixel point, will be used to prepare feux rouges amount
The reaction raw materials of son point or green light quantum point are mixed with light-cured resin system, and the black square is injected using InkJet printing processes
In the space of battle array, under the conditions of ultraviolet light, insulation reaction preset time.
2. preparation method according to claim 1, it is characterised in that the preparation method includes：
It will be mixed for the reaction raw materials for preparing red light quantum point with light-cured resin system, institute injected using InkJet printing processes
In the first space for stating black matrix", under the conditions of ultraviolet light, the preset time of insulation reaction first forms red pixel
Point；
It will be mixed for the reaction raw materials for preparing green light quantum point with light-cured resin system, institute injected using InkJet printing processes
In the Second gap for stating black matrix", under the conditions of ultraviolet light, the preset time of insulation reaction second forms green pixel
Point；
Using InkJet printing processes, by for preparing the light-cured resin system of blue pixel point injects the black matrix" the
In three spaces, ultraviolet light is carried out, blue pixel point is formed.
3. preparation method according to claim 2, it is characterised in that the red light quantum point is that granularity is 8-10nm's
CdSe；
The green light quantum point is the CdSe that granularity is 3-5nm；
First preset time is 20-30s；
Second preset time is 10-15s.
4. preparation method according to claim 3, it is characterised in that described to be used to prepare red light quantum point and green quantum
The reaction raw materials of point include：Cd precursor solutions and Se precursor solutions；
The Cd precursor solutions are：Mass ratio is 1:2-5 cadmium oleate：Octadecylene；
The Se precursor solutions are：Mass ratio is 1:5:5 selenium：Tributyl phosphate：Octadecylene, or H2Se aqueous phase solution.
5. preparation method according to claim 4, it is characterised in that when the Se precursor solutions are：Mass ratio is 1:5:5
Selenium：Tributyl phosphate：During octadecylene, the formation red pixel point or the formation green pixel point, including：
The Cd precursor solutions are well mixed with the light-cured resin system, and utilize InkJet printing processes injection described the
In one space or the Second gap, 80-110 DEG C is heated under inert atmosphere protection；
Continue to inject the Se precursor solutions into first space or the Second gap using InkJet printing processes, in purple
Under the conditions of outer light irradiation, 240-280 DEG C and the first preset time described in insulation reaction or second preset time, shape are heated to
Into the red pixel point or green pixel point.
6. preparation method according to claim 4, it is characterised in that when the Se precursor solutions are：H2Se aqueous phase solution
When, the formation red pixel point or the formation green pixel point, including：
The Cd precursor solutions are well mixed with the light-cured resin system, are placed in aqueous phase solvent, emulsifying agent is added,
Microemulsion is formed under emulsifying rate more than 15000r/min；
The microemulsion is well mixed with the Se precursor solutions, emulsified feedstock liquid is formed；
The emulsified feedstock liquid is injected in first space or the Second gap using InkJet printing processes, then, profit
Continued to inject demulsifier into first space or the Second gap with InkJet printing processes, after being demulsified, in ultraviolet light
Under the conditions of irradiation, 240-280 DEG C and the first preset time described in insulation reaction or second preset time are heated to, institute is formed
State red pixel point or green pixel point.
7. preparation method according to claim 1, it is characterised in that the formation blue pixel point, including：
Scattering particles is mixed with light-cured resin system, the 3rd space is injected using InkJet printing processes, through ultraviolet light
Irradiation, forms the blue pixel point.
8. preparation method according to claim 1, it is characterised in that described to form black matrix", bag on the transparent substrate
Include：
One layer of Cr metal level is deposited on the transparent substrate；
Using photoetching process the black matrix" is formed on the Cr metal levels.
9. a kind of quantum dot color filter, is prepared as the preparation method described in claim any one of 1-8.
10. a kind of liquid crystal panel, including the quantum dot color filter described in claim 9.
11. a kind of liquid crystal display, including the liquid crystal panel described in claim 10.
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| CN113267922A (en) * | 2020-02-17 | 2021-08-17 | 广东普加福光电科技有限公司 | Quantum dot color filter and preparation method thereof |
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