CN106848040A - A kind of preparation method of the LED quantum dot films based on 3D printing technique - Google Patents
A kind of preparation method of the LED quantum dot films based on 3D printing technique Download PDFInfo
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- CN106848040A CN106848040A CN201710201132.4A CN201710201132A CN106848040A CN 106848040 A CN106848040 A CN 106848040A CN 201710201132 A CN201710201132 A CN 201710201132A CN 106848040 A CN106848040 A CN 106848040A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/505—Wavelength conversion elements characterised by the shape, e.g. plate or foil
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
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- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of preparation method of the LED quantum dot films based on 3D printing technique, it will be uniformly blended into light-cured resin as the nano level quantum dot of color conversion medium and prints quantum dot film using 3D printing technique on substrate.Methods described is based on current development degree 3D printing technique very high, and it has the characteristics of Automated condtrol high precision, technology are applied widely, the uniform material of film forming is saved, and is particularly well-suited to the preparation of the color converted LED devices based on quantum dot.
Description
Technical field
The invention belongs to technical field of semiconductor illumination, and in particular to a kind of preparation method of quantum dot film, especially
It is related to a kind of preparation method of the LED quantum dot films based on 3D printing technique.Moreover, it relates to prepared
LED quantum dot films.
Background technology
LED (Light Emitting Diode, light emitting diode) is a kind of electroluminescent hair of semiconductor fabrication processing
Optical device, its main principle of luminosity is compound semiconductor materials under conditions of forward voltage is loaded, active electronic and hole
Compound generation photon, wherein visible component can be identified by the human eye.Compared to conventional illumination sources, LED has luminous efficiency
The advantages of height, few power consumption, reliability high and long lifespan, therefore it is considered as 21 century new light sources most with prospects.
The photochromic of LED is determined that its emission peak positions is difficult regulation, in order to obtain various ripples by the energy gap of quantum well layer
Long is photochromic, often adds fluorescent material to carry out Color Conversion when encapsulation, and such as white light LEDs are mainly and rely on blue light
LED and yellow fluorescent powder are made.But fluorescent material is still present following main problem:(1) fluorescent material is imitated in red light district
Rate is very low, it is impossible to provide very high-quality white light, its colour rendering index and visual effect are restricted;(2) particle diameter of fluorescent material exists
Micron order (generally more than 5um), particle diameter is too big, so as to cause fluorescent material to be hard to integrate in LED chip, therefore is merely able to
It is mixed into when encapsulation in resin and the surface of chip is added drop-wise to by mode for dispensing glue, but this mode is difficult control glue drop
Shape, the microscopic appearance on thickness and surface easily causes local partially yellow or partially blue uneven hot spot and occurs;(3) fluorescence
Powder proportion is too big, easily precipitates, and can be deposited inside silicones, thus can cause fluorescent material skewness, causes product
Light-emitting uniformity is poor, and color tone consistency is difficult to ensure that.
Quantum dot be a kind of three dimensions all in nanometer scale " quasi-zero dimension " nano-particle material, due to electronics and
Hole becomes discrete level structure by quantum confinement, continuous band structure, and fluorescence can be launched after being excited.As new
Luminescent material, quantum dot makes it be hopeful to substitute fluorescent material as color transition material of future generation, example with its remarkable optical characteristics
Such as, conversion efficiency higher, narrower emission peak, longer fluorescence lifetime, color stability higher etc., the characteristics of attracting most attention
Or the size of its adjustable emission peak and nanometer scale, quantum dot emission peak of today has been completely covered whole visible ray
Area, and had many researchs that quantum dot is integrated into the middle of LED chip.Existing integration mode can substantially be divided into following
It is several:(1) it is only that fluorescent material is merely substituted for quantum dot, is carried out a little with the resin of mixing quantum dot when encapsulation
Glue;(2) for organic quantum dot LED, generally quantum dot solution is spin-coated between electronics and hole transmission layer and is volatilized
Solvent film forming is used as luminescent layer;(3) LED chip is performed etching and fills quantum dot in the hole for etching.
However, first two method does not use quantum point grain diameter the characteristics of be significantly less than fluorescent material, so that using chi
It is very little to change to realize new property and application, and gluing process there is also many uncontrollable factors in itself.Further for formal dress
With the LED chip of upside-down mounting, it is impossible to which simple utilization spin coating prepares light conversion layer, and the third prepares light and turns by the method for etching
Changing layer can then reduce the area of luminous zone, the amount of the electricity structure for destroying LED chip and the quantum dot for being difficult control filling, uncomfortable
Close large-scale batch production.Above reason is based on, people are seeking in quantum dot LED technologies of preparing preferably to solve always
Certainly scheme.
The A of CN 104051599 disclose a kind of preparation method of the white-light LED fluorescence film based on 3D printing technique, its
Fluorescent material and organic resin are mixed into fluorescent powder paste material, and using 3D printing technique printed to LED chip surface or
On person remaining transparency carrier, this method can overcome the various uncontrollable factors that gluing process brings, but use in itself
Be fluorescent material, its optical property does not overcome the characteristics of such as red light district efficiency is too low, and fluorescent material particle diameter is too big, matches somebody with somebody
The fluorescence membrane for being made 3D printing after slurry is inherently difficult to accomplish very thin by the limitation of fluorescent material particle diameter, is extremely difficult to very
Accuracy high.
The A of CN 103430337 disclose a kind of LED component of utilization quantum dot, and it is provided with one in the top of LED chip
A little thin layers containing quantum dot, and be ranked up to these quantum dot layers in strict accordance with refractive index and absorption emission peak positions,
This can be such that the light of lower floor's quantum dot emission is not absorbed by upper strata, improve emission effciency, but how smart it does not provide
Really prepare the technical scheme of quantum dot thin layer.
The A of CN 104733593 disclose a kind of white light LED part based on quantum dot and preparation method thereof, and it is in LED core
Multiple graphical windows are provided with piece substrate, luminescent material is provided with light conversion layer, luminescent material includes thering is different lighting
It is separate between the quantum dot and transparent polymer material of color, the quantum dot of different glow colors to set and be covered in figure window
It is intraoral.The method can be integrated into quantum dot is real in LED chip, realizes wafer-level package, but its technology difficulty is very
The quantum dot filled if height, is difficult to realize the ultra-deep perforate on substrate, and hole is too shallow is not enough to completion coloured light very little
The need for conversion.
3D printing is a kind of rapid shaping technique, and its manufacturing technology let us can produce the thing of variously-shaped structure
Product.3D printing is by computer instruction, and the article structure layering that will be printed, then printing in layer is mutual between adjacent bed
Connection, seamlessly transits, and finally realizes total.With the development of 3D printing technique, it has printing precision high and material wave
The characteristics of taking few, and also the three-dimensional structure of various structure snd size can be printed.As a kind of advanced technology, by quantum
Point adds light-cured resin on LED chip or other substrates to prepare quantum dot film using 3D printing technique and cause many and grinds
The person's of studying carefully input great effort is studied.
The content of the invention
The purpose of the present invention is realized in order to solve the above problems, there is provided a kind of LED quantum dots based on 3D printing technique
The preparation method of film.The inventive method is easily controllable, high degree of automation, applied widely, and prepared film shape
Shape is unified, and thickness is uniform, and uniformity is good.Especially, the inventive method is applied to the system of the color converted LED devices based on quantum dot
It is standby.
To achieve these goals, present invention firstly provides a kind of LED quantum dot films based on 3D printing technique
Preparation method, it will be uniformly blended into light-cured resin as the nano level quantum dot of color conversion medium and is utilized on substrate
3D printing technique prints quantum dot film, specifically includes following steps:
(1) light-cured resin containing quantum dot is prepared:Quantum dot and light-cured resin are mixed and stirred for uniformly, to obtain
Light-cured resin containing quantum dot;
(2) slicing delamination:The computer model of the quantum dot film to be obtained is set up, and slicing delamination is carried out to it,
Obtain each layer of forming data;
(3) 3D printing:The light-cured resin containing quantum dot that step (1) is obtained imports 3D printer and by step
(2) forming data of each layer for obtaining is associated with 3D printer, is then carried out on substrate according to each layer of forming data
Successively print, finally give desired quantum dot film,
Being synchronized admittedly by the way of uv-exposure when successively being printed on substrate wherein in step (3)
Change.
By 3D printer according to calculating in the preparation method of LED quantum dot film of the present invention based on 3D printing technique
Machine control is printed on substrate, and structure graph to every layer solidifies, so as to by the Structured cured of quantum dot film
Onto substrate, moved after one layer of completion to next layer, adjacent bed figure is connected with each other, seamlessly transits, even film layer, and automation
Degree is high, practical, can realize large-scale production.
Preferably, in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, in step (1)
The mass fraction of the quantum dot in the light-cured resin containing quantum dot for being obtained is 0.2%-20%, based on containing quantum dot
Light-cured resin gross mass meter.
Preferably, in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the step
(1) species of quantum dot described in is together decided on by the intrinsic photochromic and luminous power of final required chromaticity coordinates and substrate
's.
It is highly preferred that in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the quantum
Point can be single element quantum dot, including:Au, Pd etc.;Can also be dual element quantum dot, including II-VI group element composition
Semiconducting compound such as CdS, CdSe, CdTe, MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS,
BaSe, BaTe, ZnS, ZnSe, ZnTe and its mixture, iii-v element composition semiconducting compound such as GaN, GaP,
GaAs, InN, InP, InAs and its mixture, or II-VI group element composition semiconducting compound and iii-v element group
Into semiconducting compound mixture;Can also be multielement composite quantum dot, including:Alloy-type quantum dot is (such as
CdZnSe), (such as stratum nucleare is CdSe, cadmium sulfoselenide CdSSe, indium phosphide InP to nuclear shell structure quantum point, in indium sulphur or perovskite
One or more and shell is ZnS, one or more in ZnSe, CdS or sulphur zinc impregnation cadmium CdZnS of nuclear shell structure quantum point
(such as CdSe/ZnSe, InP/ZnS)) etc..
Preferably, in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the quantum dot
Surface be connected with light-cured resin dissolubility identical part, be preferably dissolved in beneficial to quantum dot light-cured resin work as
In, free settling, the preferable film of quantum dot uniformity is not printed so as to be more convenient for.
It is highly preferred that in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the quantum
The part of the surface connection of point is oleic acid, polyethylene glycol (PEG-COOH) of carboxyl modified etc..
Preferably, in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the quantum dot
Particle diameter for 2-20nm and its emission wavelength be 380nm-780nm.
Preferably, in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the step
(1) quantum dot in can be the same structure quantum point of emission peak of the same race, or the different structure quantum of different emission peaks
The quantum dot of point, or various emission peak various structures.
Preferably, in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the step
(1) dissolubility of the quantum dot in is identical with the dissolubility of the light-cured resin.In other words, if light-cured resin is oil-soluble
, then quantum dot is oil-soluble quantum dot;If light-cured resin is water miscible, quantum dot is water-soluble quantum dot.
Preferably, in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the step
(1) light-cured resin in is the light-cured resin by all kinds that can solidify after ultraviolet photoetching, such as all kinds of third
Olefin(e) acid resin, the acrylate of acroleic acid esterification, polyurethane acrylic resin, polyester acrylate resin, polyoxyalkylene acrylate
Resin, epoxy resin and vinyl ether resin.
Preferably, in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the step
(3) substrate in is LED chip or other substrates.
It is highly preferred that in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the LED
Chip is packed LED chip, flip LED chips, the LED chip of vertical stratification or organic LED chip.
It is highly preferred that the present invention based on 3D printing technique LED quantum dot films preparation method in, it is described other
Substrate includes but is not limited to glass, ceramics, plastics, acrylic, PC etc., and its shape can be plane or curved.
Preferably, in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, the step
(3) condition of the uv-exposure in is that light intensity is 30-150mW/cm2And the time is 0.1-100s.Specific uv-exposure condition
Preferentially chosen with the species of light-cured resin.
Preferably, in the preparation method of LED quantum dot film of the present invention based on 3D printing technique, prepared by the present invention
The thickness range of LED quantum dot films be 5nm-5mm.The thickness of specific quantum dot film is according to the LED to be obtained
Size and performance determine.
Additionally, present invention also offers a kind of LED quantum dot films prepared by the above method.
Compared with prior art, the present invention has advantages below and beneficial effect:
(1) what preparation method of the present invention can be real carries out the film painting of micron even nanoscale on LED chip surface
Cover, realize the wafer-level package of real meaning, while some optics knots can also be prepared in chip surface using 3D printing technique
Structure, such as collimation lens etc..Its technology difficulty is more prone to realization for filling quantum dot compared to etching chip, and can
More precisely control.
(2) preparation method of the present invention prepares quantum dot film using 3D printing technique, the quantum that can be prepared with precise control
The shape and structure size of point film, can effectively lift the uniformity and uniformity of quantum dot film, it is to avoid in gluing process
The non-uniform light that various uncontrollable factors are caused, the phenomenon such as colour temperature is inconsistent.
(3) preparation method of the present invention can be also used for being prepared on other substrates the quantum dot film of micro/nano-scale, can be with
LED product for preparing long-range quantum dot layer, and methods described is based on current development degree 3D printing technique very high, its tool
There is the features such as Automated condtrol high precision, technology are applied widely, film forming is uniform, material is saved, be particularly well-suited to based on quantum
The preparation of the color converted LED devices of point.
Specific embodiment
In order to more easily understand the present invention, below in conjunction with embodiment present disclosure further elucidated above, but this
The content of invention is not limited only to embodiments discussed below.
Embodiment 1
By emission peak for 520nm with PEG-COOH (polyethylene glycol of carboxyl modified) for ligand i nP/ZnS core shell structures
Green light quantum point and emission peak are for 570nm with PEG-COOH (polyethylene glycol of carboxyl modified) for ligand i nP/ZnS nucleocapsid knots
Structure gold-tinted quantum dot 8:5 are mixed into hydrophilic light-cured resin epoxy resin, stir, the light containing quantum dot for being obtained
The mass fraction of the quantum dot in solidified resin is 5%.
The computer model of the structure and morphology of the quantum dot film required for setting up on computers, and it is cut into slices
Layering, obtains each layer of forming data, and the forming data of each layer for then obtaining is imported in 3D printer, while will match somebody with somebody
The charging tray that the light-cured resin containing quantum dot is added to 3D printer is made, then according to each layer of forming data in conduct
The emission peak of substrate the blue light packed LED chip of 450nm or so front print quantum dot film, and printing when with light intensity
It is 50mW/cm2Ultraviolet photoetching 5s desired quantum dot film is obtained final product to be solidified, after the completion of printing, what it was obtained
Except p-electrode and the whole uniform thickness covering of remaining region of n-electrode, solidification anteroposterior dimension is consistent quantum dot film, and thickness
It is thickness set in advance, specially 3 μm.
By being printed with of being obtained after the blue light packed LED chip of green glow and gold-tinted quantum dot film is powered and lights, LED
Light field is uniform, is tested by spectrum and chromaticity coordinate and is no less than 100 LEDs chips, and by being analyzed meter to the curve of spectrum
Calculate, its chromaticity coordinates position in white light field, and with batch with condition LED chip chromaticity coordinates position, colour rendering index, colour temperature with it is each
From average value be less than 2%.
Embodiment 2
By emission peak for 450nm with PEG-COOH (polyethylene glycol of carboxyl modified) for ligand i nP/ZnS core shell structures
Blue light quantum point, emission peak are for 520nm with PEG-COOH (polyethylene glycol of carboxyl modified) for ligand i nP/ZnS core shell structures
Green light quantum point and emission peak are for 620nm with PEG-COOH (polyethylene glycol of carboxyl modified) for ligand i nP/ZnS nucleocapsid knots
Structure red quantum presses 1:1:1 ratio is mixed into hydrophilic light-cured resin epoxy resin, stirs, and what is obtained contains
The mass fraction of the quantum dot in the light-cured resin of quantum dot is 1%.
The computer model of the structure and morphology of the quantum dot film required for setting up on computers, and it is cut into slices
Layering, obtains each layer of forming data, and the forming data of each layer for then obtaining is imported in 3D printer, while will match somebody with somebody
The charging tray that the light-cured resin containing quantum dot is added to 3D printer is made, then according to each layer of forming data in conduct
The emission peak of substrate prints quantum dot film on the backing substrate of the ultraviolet flip LED chips of 365nm or so, and in printing
With light intensity as 50mW/cm2Ultraviolet photoetching 5s desired quantum dot film is obtained final product to be solidified, after the completion of printing, its institute
The region-wide uniform thickness covering of quantum dot film of acquisition, solidification anteroposterior dimension is consistent, and thickness is thickness set in advance,
Specially 6 μm.
To obtain be printed with the ultraviolet flip LED chips of blue and green light and red light quantum point film be powered light after,
LED light field is uniform, is tested by spectrum and chromaticity coordinate and is no less than 100 LEDs chips, and with the LED chip color seat of batch
Cursor position, colour rendering index, colour temperature is less than 2% with respective average value.
Embodiment 3
By emission peak for 450nm with PEG-COOH (polyethylene glycol of carboxyl modified) for ligand i nP/ZnS core shell structures
Blue light quantum point, emission peak are for 520nm with PEG-COOH (polyethylene glycol of carboxyl modified) for ligand i nP/ZnS core shell structures
Green light quantum point and emission peak are for 620nm with PEG-COOH (polyethylene glycol of carboxyl modified) for ligand i nP/ZnS nucleocapsid knots
Structure red quantum presses 1:1:1 ratio is mixed into hydrophilic light-cured resin epoxy resin, stirs, and what is obtained contains
The mass fraction of the quantum dot in the light-cured resin of quantum dot is 1%.
The computer model of the structure and morphology of the quantum dot film required for setting up on computers, and it is cut into slices
Layering, obtains each layer of forming data, and the forming data of each layer for then obtaining is imported in 3D printer, while will match somebody with somebody
The charging tray that the light-cured resin containing quantum dot is added to 3D printer is made, then according to each layer of forming data in conduct
The thickness of substrate is the transparent plastic printing quantum dot film of 0.01mm, and in printing with light intensity as 50mW/cm2Ultraviolet light
Exposure 5s is solidified, and desired quantum dot film is obtained final product after the completion of printing, the region-wide uniform thickness of the quantum dot film that it is obtained
Covering, solidification anteroposterior dimension is consistent, and thickness is thickness set in advance, specially 5 μm.
The transparent plastic substrate of printed quantum dot film is arranged on the ultraviolet LED core of vertical stratification in packaging technology
The top of piece, as long-range color converting layer, subsequently powers on after lighting, and LED light field is uniform, is tested by spectrum and chromaticity coordinate
No less than 100 LEDs chips, by being analyzed calculating to the curve of spectrum, with the LED chip chromaticity coordinates position of batch, colour developing
Index, colour temperature is less than 2% with respective average value.
Claims (10)
1. a kind of preparation method of the LED quantum dot films based on 3D printing technique, it is using as the nanometer of color conversion medium
The quantum dot of level is uniformly blended into light-cured resin and prints quantum dot film using 3D printing technique on substrate, specifically includes
Following steps:
(1) light-cured resin containing quantum dot is prepared:Quantum dot and light-cured resin are mixed and stirred for uniformly, to be contained
The light-cured resin of quantum dot;
(2) slicing delamination:The computer model of the quantum dot film to be obtained is set up, and slicing delamination is carried out to it, obtained
Each layer of forming data;
(3) 3D printing:The light-cured resin containing quantum dot that step (1) is obtained is imported into 3D printer and step (2) is obtained
The forming data of each layer for arriving is associated with 3D printer, is then successively beaten on substrate according to each layer of forming data
Print, finally gives desired quantum dot film,
Solidification is wherein synchronized by the way of uv-exposure when successively being printed on substrate in step (3).
2. a kind of preparation method of LED quantum dot films based on 3D printing technique according to claim 1, its feature
It is that the species of quantum dot described in the step (1) is the intrinsic photochromic and light work(by final required chromaticity coordinates and substrate
What rate was together decided on.
3. a kind of preparation method of LED quantum dot films based on 3D printing technique according to claim 2, its feature
It is that the quantum dot in the step (1) can be the same structure quantum point of emission peak of the same race, the different structure of different emission peaks
The quantum dot of quantum dot or various emission peak various structures.
4. a kind of preparation method of LED quantum dot films based on 3D printing technique according to claim 3, its feature
It is that the dissolubility of the quantum dot in the step (1) is identical with the dissolubility of the light-cured resin.
5. a kind of preparation method of LED quantum dot films based on 3D printing technique according to claim 1, its feature
It is that the light-cured resin in the step (1) is the photocuring by all kinds that can solidify after ultraviolet photoetching
Resin.
6. a kind of preparation method of LED quantum dot films based on 3D printing technique according to claim 1, its feature
It is that the substrate in the step (3) is LED chip or other substrates.
7. a kind of preparation method of LED quantum dot films based on 3D printing technique according to claim 6, its feature
It is that the LED chip is packed LED chip, flip LED chips, the LED chip or organic LED chip of vertical stratification.
8. a kind of preparation method of LED quantum dot films based on 3D printing technique according to claim 1, its feature
It is that the condition of the uv-exposure in the step (3) is fully cured by light-cured resin used and is defined.
9. a kind of preparation method of LED quantum dot films based on 3D printing technique according to claim 1, its feature
The thickness range for being the LED quantum dot films for being obtained is 5nm-5mm.
10. the preparation of a kind of LED quantum dot films based on 3D printing technique by any one of claim 1-9
LED quantum dot films prepared by method.
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TWI701284B (en) * | 2018-03-26 | 2020-08-11 | 南韓商東友精細化工有限公司 | A light converting resin composition, a light converting laminated substrate and a display device using the same |
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