CN104449738B - Cellulose and semi-conductor nano particles compound, preparation method and the application in LED encapsulates - Google Patents
Cellulose and semi-conductor nano particles compound, preparation method and the application in LED encapsulates Download PDFInfo
- Publication number
- CN104449738B CN104449738B CN201410578626.0A CN201410578626A CN104449738B CN 104449738 B CN104449738 B CN 104449738B CN 201410578626 A CN201410578626 A CN 201410578626A CN 104449738 B CN104449738 B CN 104449738B
- Authority
- CN
- China
- Prior art keywords
- semi
- cellulose
- nano particles
- conductor nano
- led
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
Cellulose and semi-conductor nano particles compound, preparation method and the application in LED encapsulates, belong to LED encapsulation material technical field, it is specifically related under a kind of low temperature under LiOH/ urea booster action compound and the preparation method of compound formed in semi-conductor nano particles solution by cellulose dissolution, the method is by regulation semi-conductor nano particles size, kind, concentration, can obtain and there is different fluorescence color in a large number, the complex solution of high stability, after complex solution at room temperature places the short time simultaneously, may be formed into variously-shaped body phase material, can be used in LED encapsulation material, and then obtain the LED light source of high-color rendering.The kind of nano particle is CdTe, CdSe, CdS or CdSexTe1‑x, a size of 2.1～5.2 nanometers, the mass ratio of LiOH, urea, semi-conductor nano particles solution and cellulose is 1.4～2.6:2.6～5:12.5～25:1.
Description
Technical field
The invention belongs to LED encapsulation material technical field, be specifically related to cellulose dissolution under a kind of low temperature in partly leading
The compound of body nano-particle solution formation and the preparation method of compound, the method is by regulation semiconductor nano grain
Sub-size, kind, concentration, can obtain the complex solution in a large number with different fluorescence color, high stability,
After complex solution at room temperature places the short time simultaneously, may be formed into variously-shaped body phase material.This compound
Can apply in LED encapsulation material, and then obtain the LED light source of high-color rendering.
Background technology
Light emitting diode (LED) light source, as the solid light source that a class is emerging, its life-span length and light efficiency are high.When
Before, LED life was up to 100,000 hours, and this is fresh with formation in 10,000 hours of the 1000 of incandescent lamp hours and fluorescent lamp
Bright contrast, and luminous efficiency has broken through 300lm/W, compared to the 16lm/W of conventional fluorescent tube and fluorescent tube
70lm/W demonstrates the biggest advantage.Power consumption due to the most about 1/4th is all used to illumination, institute
If to use LED will be greatly saved the energy, researcher predicts, after using LED as lighting source,
The whole world just can reduce about 4.2 × 10 every year8The discharge capacity of ton carbon dioxide.At present, the structure master of LED component
It is divided into two classes: self-luminous (electroluminescent) device and active light emissive (photic) device.First kind device limits due to technology,
It is difficult to mass market.Relative to selfluminous element, active light emissive device is except including that electroluminescent is blue light
Outside LED lamp, also including the encapsulating material being mixed with fluorescent material, LED mostly is this class formation in the market.
But, it being limited to the dissolubility of encapsulating material, in commercially available LED, fluorescent material mostly is rare earth material, and its price is held high
Expensive, spectrum controllability is low so that this LED increasingly can not meet the requirement of people.Especially show at display
Look aspect, its deficiency is especially prominent, and this is also the bottleneck encountered in current LED light source development process.Solve
Problem it is crucial that invent a kind of new fluorescence composite material, much attempt energetically to this end, people have done.
In numerous fluorescent materials, semi-conductor nano particles is owing to having narrow half-peak breadth, high-quantum efficiency, wide absorption
The unique advantages such as band, thus become the most promising candidate material of class.But it is many to be limited to traditional encapsulating material
For oil-soluble polymers so that the quantum dot of the employing quantum dot that generally prepared by oil phase method, this results in and produces into
Originally increase substantially, it is impossible to the problem of volume production.Therefore, find a kind of based on aqueous-phase semiconductor nano particle compound
Material is the key solving this problem.
Summary of the invention
It is an object of the invention to provide a kind of easy and simple to handle and cost lower based on semi-conductor nano particles and fiber
The composite of element compound, the most first synthesizes the semi-conductor nano particles solution of various fluorescence color, then at LiOH/
Under urea and low temperature booster action, by cellulose dissolution in wherein, finally it is applied to prepare the white of high-color rendering
In light LED light source.
The present invention utilizes aqueous synthesis method, and early stage first obtains the semi-conductor nano particles aqueous solution of different fluorescence color,
Subsequently under LiOH/ urea and low temperature booster action, cellulose dissolution is had certain viscosity in wherein formation and is combined
Thing solution.After this complex solution at room temperature places the short time, can be formed have high fluorescence quantum efficiency,
Adjustable fluorescence color, the composite of high stability.Therefore, it is possible to as color conversion layer, be applied to LED
Encapsulating material in.Meanwhile, by regulate and control semi-conductor nano particles fluorescence color, can produce high-color rendering,
High brightness, the white LED light source of adjustable color.
The raw material that the present invention uses is all the commercial inorganic salts that can have directly bought and cellulose, it is not necessary to further
Processing, the most directly mix, therefore experimental implementation is easy, dangerous little, and has good
Experimental repeatability, can produce in batches, the composite simultaneously obtained has high fluorescence quantum efficiency.Use
LED light source is the commercial unencapsulated naked paster of blue-ray LED 5050.
Above-mentioned water-soluble II-VI group nano particle building-up process patent previously there is detailed explanation, the most not
Repeat again.The semi-conductor nano particles used in the present invention mainly includes CdTe, CdSe, CdS and CdSexTe1-x
Nano particle (0 < x < 1), the part of these nano particles can be mercaptopropionic acid, TGA or mercapto glycerol.
The step preparing compound in the present invention is as follows:
In unlimited system, the different fluorescence color of addition, concentration are 1.0 × 10-3～0.1mol/L (belongs to GOLD FROM PLATING SOLUTION
Cd constituent content calculate) CdTe, CdSe, CdS or CdSexTe1-xSemi-conductor nano particles solution, then
Dissolve LiOH and urea wherein, be placed in-20～the environment of-12 DEG C in, when its temperature stabilization, add fiber
Element, and be stirred vigorously and make it dissolve, i.e. obtain complex solution；Then being added drop-wise to material is poly-methylpropanoic acid methyl esters
Mould in, mould be shaped as cylinder, square and " Jilin University " four Chinese characters, at room temperature put
After putting 3～5 hours, the i.e. available composite identical with mold shape.Also complex solution can be coated in not
On the LED of encapsulation, more at room temperature place after 3～5 hours, i.e. obtain packaged LED light source.Reactant
In system, the size of nano particle is 2.1～5.2 nanometers, and the molecular weight of cellulose is 8.0 × 104～1.0 × 105, meanwhile,
LiOH, urea, nano-particle solution, the mass ratio of cellulose are 1.4～2.6:2.6～5:12.5～25:1.
Accompanying drawing explanation
Fig. 1: having of utilizing prepared by the stable CdTe nano particle of mercaptopropionic acid and the compound of cellulose is orange
(a), green (b), yellow (c), the body phase material of red (d) fluorescence；
Fig. 2: the CdTe nano particle utilizing mercaptopropionic acid stable prepare from the compound of cellulose containing different dense
The body phase material of degree nano particle, illustrates nano-particle solution concentration, can prepare containing variable concentrations nanometer
The body phase material of particle；
Fig. 3: having of utilizing prepared by the stable CdTe nano particle of mercapto glycerol and the compound of cellulose is green glimmering
The body phase material (a) of light, fluorescence spectrum (b) corresponding thereto, fluorescence spectrum shows that body phase material maintains nanoparticle
The luminosity of son；
Fig. 4: utilize prepared by the stable CdTe nano particle of TGA and the compound of cellulose to have yellow glimmering
The body phase material (a) of light, fluorescence spectrum (b) corresponding thereto, fluorescence spectrum shows that body phase material maintains nanoparticle
The luminosity of son；
Fig. 5: utilize the mercaptopropionic acid stable CdTe nano particle composite with cellulose as encapsulating material system
Standby luminescence is the LED area light source (a) of green glow, CIE coordinate (b) of LED light source, its CIE coordinate be (0.28,
0.44), illustrate to utilize this composite can prepare the luminous LED light source for green glow；
Fig. 6: utilize the mercaptopropionic acid stable CdTe nano particle composite with cellulose as encapsulating material system
Standby luminescence is the LED area light source (a) of gold-tinted, CIE coordinate (b) of LED light source, its CIE coordinate be (0.54,
0.43), illustrate to utilize this composite can prepare the luminous LED light source for gold-tinted；
Fig. 7: utilize the mercaptopropionic acid stable CdTe nano particle composite with cellulose as encapsulating material system
Standby luminescence is the LED area light source (a) of orange light, CIE coordinate (b) of LED light source, its CIE coordinate be (0.58,
0.37), illustrate to utilize this composite can prepare the luminous LED light source for orange light；
Fig. 8: utilize the mercaptopropionic acid stable CdTe nano particle composite with cellulose as encapsulating material system
Standby luminescence is the LED area light source (a) of ruddiness, CIE coordinate (b) of LED light source, its CIE coordinate be (0.65,
0.33), illustrate to utilize this composite can prepare the luminous LED light source for ruddiness；
Fig. 9: utilize and there is being combined of the stable CdTe nano particle of the mercaptopropionic acid of different fluorescence color and cellulose
The LED light source (a) that luminescence is white light that material is prepared as encapsulating material, the luminescent spectrum (b) of LED light source and
Its CIE coordinate (c), its CIE coordinate is (0.34,0.32), illustrate by mix fluorescence color the most of the same race from group
It is the LED light source of white light that package material can prepare transmitting light.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further elaborated rather than to limit the invention with this.
Embodiment 1
Take CdTe nano-particle solution (its stable by mercaptopropionic acid of a diameter of 2.1,2.6,3.1 and 5.2 nanometers
The concentration of middle Cd element is 1.0 × 10-3Mol/L) each 2mL, is separately added into LiOH's and 0.42g of 0.22g
Urea, after dissolving, after being cooled to-12 DEG C, addition 0.16g, molecular weight are 8.0 × 104Cellulose, and
It is stirred vigorously and makes it dissolve, then complex solution is put in difform mould, after 2 hours, such as Fig. 1
Shown in, obtain the difform composite with hyperfluorescence.
Embodiment 2
Taking concentration is 0.1,5.0 × 10-2、2.0×10-2、5.0×10-3With 1.0 × 10-3A diameter of 2.8 nanometers of mol/L
The CdTe nano-particle solution each 2mL stable by mercaptopropionic acid, is separately added into LiOH and 0.42g of 0.22g
Urea, after dissolving, after being cooled to-20 DEG C, adding 0.16g, molecular weight is 8.0 × 104Cellulose,
And be stirred vigorously and make it dissolve, then complex solution is put in mould, after 2 hours, as in figure 2 it is shown,
To the composite containing variable concentrations nano particle, its color is along with the increase of nanoparticle concentration is from faint yellow turn
Become buff.And utilize elementary analysis instrument, wherein Cd element is carried out quantitative analysis, along with nano particle
The increase of concentration, Cd content is also being on the increase (such as table 1).
Table 1: the content of Cd in the composite that the CdTe nano-particle solution of variable concentrations prepares
Embodiment 3
(wherein Cd constituent content is by the stable CdTe nano-particle solution of mercapto glycerol to take a diameter of 2.2 nanometers
2.0×10-3Mol/L) 2mL, adds the urea of LiOH and 0.4g of 0.21g, after dissolving, is cooled to-12 DEG C
After, addition 0.08g, molecular weight are 1.0 × 105Cellulose, and be stirred vigorously and make it dissolve, then by compound
Solution is put in mould, after 2 hours, as shown in Figure 3 a, obtains the composite with green fluorescence.And utilize
XRF, tests its fluorescence emission spectrum, as shown in Figure 3 b.
Embodiment 4
(wherein Cd constituent content is by the stable CdTe nano-particle solution of TGA to take a diameter of 2.5 nanometers
2.0×10-3Mol/L) 2mL, adds the urea of LiOH and 0.42g of 0.22g, after dissolving, is cooled to
After-12 DEG C, add 0.16g, molecular weight is 1.0 × 105Cellulose, and be stirred vigorously and make it dissolve, then will
Complex solution is put in mould, after 2 hours, as shown in fig. 4 a, obtains the composite with yellow fluorescence.
And utilize XRF, test its fluorescence emission spectrum, as shown in Figure 4 b.
Embodiment 5
(wherein Cd constituent content is by the stable CdTe nano-particle solution of mercaptopropionic acid to take a diameter of 2.1 nanometers
2.0×10-2Mol/L) 2mL, adds the urea of LiOH and 0.42g of 0.22g, after dissolving, is cooled to
After-12 DEG C, the molecular weight adding 0.16g is 1.0 × 105Cellulose, and be stirred vigorously and make it dissolve, be then coated with
Overlaying on unencapsulated LED, coating thickness is 2 millimeters, after ambient temperatare puts 5 hours, obtains luminous for green glow
LED light source (Fig. 5 a).
Embodiment 6
(wherein Cd constituent content is by the stable CdTe nano-particle solution of mercaptopropionic acid to take a diameter of 2.4 nanometers
2.0×10-2Mol/L) 2mL, adds the urea of LiOH and 0.42g of 0.22g, after dissolving, is cooled to
After-12 DEG C, the molecular weight adding 0.16g is 1.0 × 105Cellulose, and be stirred vigorously and make it dissolve, be then coated with
Overlaying on unencapsulated LED, coating thickness is 2 millimeters, after ambient temperatare puts 5 hours, obtains luminous for gold-tinted
LED light source (Fig. 6 a).
Embodiment 7
(wherein Cd constituent content is by the stable CdTe nano-particle solution of mercaptopropionic acid to take a diameter of 2.9 nanometers
2.0×10-2Mol/L) 2mL, adds the urea of LiOH and 0.42g of 0.22g, after dissolving, is cooled to
After-12 DEG C, the molecular weight adding 0.16g is 1.0 × 105Cellulose, and be stirred vigorously and make it dissolve, be then coated with
Overlaying on unencapsulated LED, coating thickness is 2 millimeters, after ambient temperatare puts 5 hours, obtains luminous for orange light
LED light source (Fig. 7 a).
Embodiment 8
(wherein Cd constituent content is by the stable CdTe nano-particle solution of mercaptopropionic acid to take a diameter of 3.6 nanometers
2.0×10-2Mol/L) 2mL, adds the urea of LiOH and 0.42g of 0.22g, after dissolving, is cooled to
After-12 DEG C, the molecular weight adding 0.16g is 1.0 × 105Cellulose, and be stirred vigorously and make it dissolve, be then coated with
Overlaying on unencapsulated LED, coating thickness is 2 millimeters, after ambient temperatare puts 5 hours, obtains luminous for ruddiness
LED light source (Fig. 8 a).
Embodiment 9
Take a diameter of 2.2 and 4.1 nanometers by stable CdTe nano-particle solution (the wherein Cd element of mercaptopropionic acid
Content is 2.0 × 10-2Mol/L) each 2mL, then it is separately added into the urea of LiOH and 0.42g of 0.22g, molten
Xie Hou, after being cooled to-12 DEG C, the molecular weight adding 0.16g is 1.0 × 105Cellulose, and be stirred vigorously
It is made to dissolve, then successively by redness (wherein nano-particles size is 4.1 nanometers) and green (wherein nanoparticle
Son a size of 2.2 nanometer) fluorescence composite material is coated on unencapsulated LED, red and Green Composites
Coating thickness is respectively 0.4 and 1.6 millimeter, after ambient temperatare puts 5 hours, obtains the luminous LED light for white light
Source (Fig. 9 a).Red and green fluorescence composite mass ratio is 1:4.
Claims (5)
1. a cellulose and the preparation method of semi-conductor nano particles compound, it is characterised in that: to utilizing water
Semi-conductor nano particles solution prepared by the method for being combined to dissolves LiOH and urea, is placed in-20～-12 DEG C
Environment in, when its temperature stabilization, add cellulose, and be stirred vigorously and make it dissolve, i.e. obtain
Semi-conductor nano particles complex solution；Then it is added drop-wise in mould, at room temperature places 3～5 hours
After, the i.e. available composite identical with mold shape；In above-mentioned reaction system, semiconductor nano
The size of particle is 2.1～5.2 nanometers, and the molecular weight of cellulose is 8.0 × 104～1.0 × 105, LiOH,
Urea, nano-particle solution, the mass ratio of cellulose are 1.4～2.6:2.6～5:12.5～25:1；Water
Semi-conductor nano particles prepared by the method for being combined to is CdTe, CdSe, CdS or CdSexTe1-xNanometer
Particle；Calculating with Cd constituent content in solution, semi-conductor nano particles prepared by aqueous synthesis method is molten
The concentration of liquid is 1.0 × 10-3～0.1mol/L.
A kind of cellulose the most as claimed in claim 1 and the preparation method of semi-conductor nano particles compound, its
It is characterised by: the part of semi-conductor nano particles prepared by aqueous synthesis method is mercaptopropionic acid, sulfydryl
Acetic acid or mercapto glycerol.
3. a cellulose and semi-conductor nano particles compound, it is characterised in that: any by claim 1～2
One described method prepares.
4. the cellulose described in claim 3 and the semi-conductor nano particles compound application in LED encapsulates.
5. cellulose as claimed in claim 4 and the semi-conductor nano particles compound application in LED encapsulates,
It is characterized in that: be complex solution to be coated on unencapsulated LED, at room temperature place 3～5
After hour, i.e. obtain packaged LED.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410578626.0A CN104449738B (en) | 2014-10-23 | 2014-10-23 | Cellulose and semi-conductor nano particles compound, preparation method and the application in LED encapsulates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410578626.0A CN104449738B (en) | 2014-10-23 | 2014-10-23 | Cellulose and semi-conductor nano particles compound, preparation method and the application in LED encapsulates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104449738A CN104449738A (en) | 2015-03-25 |
| CN104449738B true CN104449738B (en) | 2016-08-24 |
Family
ID=52896504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410578626.0A Expired - Fee Related CN104449738B (en) | 2014-10-23 | 2014-10-23 | Cellulose and semi-conductor nano particles compound, preparation method and the application in LED encapsulates |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104449738B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751583A (en) * | 2016-12-27 | 2017-05-31 | 铜陵市铜峰光电科技有限公司 | A kind of LED fire-retardant plastics of high heat conduction of the adjustable iridescent of cellulose CdTe and preparation method thereof |
| CN107474474A (en) * | 2017-07-27 | 2017-12-15 | 中国林业科学研究院林产化学工业研究所 | A kind of cellulose enhancing phenolic resin composite and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560633A (en) * | 2004-02-19 | 2005-01-05 | 上海交通大学 | Preparation method of quantum point microspheric for bio-medical fluorescence probe |
| CN101423614B (en) * | 2008-11-14 | 2011-04-20 | 武汉大学 | Luminescent fibre hydrogel and preparation method thereof |
| GB201005601D0 (en) * | 2010-04-01 | 2010-05-19 | Nanoco Technologies Ltd | Ecapsulated nanoparticles |
| CN102336928B (en) * | 2011-07-08 | 2012-11-28 | 北京理工大学 | Flexible, environmentally-friendly, transparent and adjustable-illuminant-color film material and preparation method thereof |
-
2014
- 2014-10-23 CN CN201410578626.0A patent/CN104449738B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104449738A (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Self‐quenching‐resistant red emissive carbon dots with high stability for warm white light‐emitting diodes with a high color rendering index | |
| Wang et al. | White light-emitting devices based on carbon dots’ electroluminescence | |
| Ma et al. | Facile, controllable tune of blue shift or red shift of the fluorescence emission of solid-state carbon dots | |
| Sun et al. | Combination of carbon dot and polymer dot phosphors for white light-emitting diodes | |
| Tang et al. | Enhancement of luminous efficiency and uniformity of CCT for quantum dot-converted LEDs by incorporating with ZnO nanoparticles | |
| Wang et al. | Polymer-assisted self-assembly of multicolor carbon dots as solid-state phosphors for fabrication of warm, high-quality, and temperature-responsive white-light-emitting devices | |
| Zhai et al. | Red carbon dots-based phosphors for white light-emitting diodes with color rendering index of 92 | |
| CN108018039B (en) | Preparation method and application of white light emitting carbon quantum dots | |
| CN106025042A (en) | Stable white-light LED based on silicon dioxide coated perovskite quantum dots, and preparation method thereof | |
| CN103773364B (en) | Preparation method of bicolor fluorescent semiconductor nanomaterial based on Mn-doped CuInS2/ZnS | |
| CN108795423B (en) | Preparation method of high-quantum-yield solid carbon dot fluorescent powder and application of fluorescent powder in LED lamp beads | |
| CN108251117A (en) | Core-shell quanta dots and preparation method thereof and the electroluminescent device containing it | |
| WO2007034877A1 (en) | Semiconductor nanoparticles dispersed glass fine particles and process for preparing the same | |
| CN107053780A (en) | A kind of quantum dot film being applied in backlight module and preparation method thereof | |
| CN105152147A (en) | Method for preparation of water-soluble luminous graphite-phase carbon nitride nano kelp | |
| Deng et al. | Solid-state thiolate-stabilized copper nanoclusters with ultrahigh photoluminescence quantum yield for white light-emitting devices | |
| CN105304799A (en) | Method for preparing LEDs with different light colors based on metal nano-cluster packaging material | |
| CN105576106A (en) | InP/ZnS quantum dot and CIS/ZnS quantum dot for white-light LED and preparation method of InP/ZnS quantum dot and CIS/ZnS quantum dot | |
| Yin et al. | The thermal stability performances of the color rendering index of white light emitting diodes with the red quantum dots encapsulation | |
| Lu et al. | Combination of chemical etching of gold nanoclusters with aggregation-induced emission for preparation of new phosphors for the development of UV-driven phosphor-converted white light-emitting diodes | |
| Chen et al. | Red C-dots and C-dot films: solvothermal synthesis, excitation-independent emission and solid-state-lighting | |
| CN106098905A (en) | The method of the synthesis of stream continuously of the polymer pad that core-shell structure copolymer is quantum dot-doped and the method for the emission spectrum of correction light-emitting device | |
| CN104449738B (en) | Cellulose and semi-conductor nano particles compound, preparation method and the application in LED encapsulates | |
| CN107722291B (en) | Rare earth-organic framework material with organic dye introduced and preparation method thereof | |
| Kwon et al. | Plasmonic-enhanced luminescence characteristics of microscale phosphor layers on a ZnO nanorod-arrayed glass substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 Termination date: 20181023 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |