CN105969348B - A kind of carbon nano-point phosphor, preparation method and LED lamp bead - Google Patents
A kind of carbon nano-point phosphor, preparation method and LED lamp bead Download PDFInfo
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- CN105969348B CN105969348B CN201610344825.4A CN201610344825A CN105969348B CN 105969348 B CN105969348 B CN 105969348B CN 201610344825 A CN201610344825 A CN 201610344825A CN 105969348 B CN105969348 B CN 105969348B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 198
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000011324 bead Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002096 quantum dot Substances 0.000 claims abstract description 111
- 239000000463 material Substances 0.000 claims abstract description 56
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 30
- 159000000009 barium salts Chemical class 0.000 claims abstract description 30
- 238000000605 extraction Methods 0.000 claims abstract description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 24
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 18
- 229910001626 barium chloride Inorganic materials 0.000 claims description 18
- 229910001422 barium ion Inorganic materials 0.000 claims description 15
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 150000002500 ions Chemical group 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical group [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- -1 polydimethylsiloxanes Polymers 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000002776 aggregation Effects 0.000 abstract description 6
- 238000004220 aggregation Methods 0.000 abstract description 6
- 230000001939 inductive effect Effects 0.000 abstract description 5
- 230000000171 quenching effect Effects 0.000 abstract description 5
- 238000005119 centrifugation Methods 0.000 description 29
- 238000003756 stirring Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000007832 Na2SO4 Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 241001062009 Indigofera Species 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- VUTSITSGGYCKFP-UHFFFAOYSA-J [C+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [C+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VUTSITSGGYCKFP-UHFFFAOYSA-J 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
This application discloses a kind of carbon nano-point phosphor, the application of preparation method and carbon nano-point phosphor in LED lamp bead, wherein, carbon nano dot surface of the carbon nano-point phosphor preparation method by way of solvable barium salt and solvable sulfate are added in carbon nanodot solution in the carbon nanodot solution forms stable barium sulfate.The barium sulfate plays a part of isolating between carbon nano dot during the pending mixed liquor is carried out extraction process reunites, so that the carbon nano dot will not lose fluorescent characteristic due to aggregation inducing fluorescent quenching effect, precondition is created to obtain the carbon nano-point phosphor.And due to the preferable stability of barium sulfate and the strong fluorescent properties of carbon nano dot so that the carbon nano-point phosphor prepares material as preferable LED lamp bead color conversion layer.
Description
Technical field
The present invention relates to technical field of nano material, more specifically to a kind of carbon nano-point phosphor, preparation method
And LED lamp bead.
Background technology
Light emitting diode (Light Emitting Diode, LED) lamp bead is a kind of emerging solid light source, and its energy is sharp
Reach the 14%-15% of gross energy with rate, far above incandescent lamp and fluorescent lamp, and its service life and luminous efficiency compared to
Incandescent lamp and fluorescent lamp also have greater advantage.
The primary structure of LED lamp bead includes active luminescent device (LED chip) at present, and wraps up the LED chip
Encapsulating material, fluorescent material is mixed with the encapsulating material.But the main component in the fluorescent material of main flow is rare earth luminous at present
Material, and rare earth luminescent material has the shortcomings that non-renewable and expensive so that LED lamp bead is further applied by office
Limit.There is researcher in recent years and the rare earth luminescent material is substituted by using semi-conductor nano particles as the fluorescent material
Main component, although the semi-conductor nano particles without rare earth luminescent material it is non-renewable the shortcomings that, its toxicity
It is larger, cost is higher.
Carbon nano dot has high stability, low preparation cost, Gao Ying as a kind of novel fluorescence material based on carbon material
The advantage of photo-quantum efficiency, low bio-toxicity, turn into the fluorescent material with wide application prospect.But carbon nano dot is gone back at present
It is concentrated mainly in solution and applies, can be lost when carbon nanodot solution is condensed into solid-state due to aggregation inducing fluorescent quenching effect
Deblooming characteristic, so as to fluorescent material is used as to be applied in LED lamp bead.
Therefore, a kind of one of direction that method for preparing carbon nano-point phosphor is made great efforts as researcher is found
The content of the invention
In order to solve the above technical problems, the invention provides a kind of carbon nano-point phosphor, preparation method and LED lamp bead,
To realize the purpose for preparing the carbon nano-point phosphor with fluorescent characteristic.
To realize above-mentioned technical purpose, the embodiments of the invention provide following technical scheme：
A kind of carbon nano-point phosphor preparation method, including：
Obtain carbon nanodot solution；
Solvable barium salt and solvable sulfate are dissolved in the carbon nanodot solution, obtain pending mixed liquor, it is described
Wrapped up by barium sulfate on carbon nano dot surface in pending mixed liquor；
Extraction process is carried out to the pending mixed liquor, obtains carbon nano-point phosphor.
Preferably, it is described that solvable barium salt and solvable sulfate are dissolved in the carbon nanodot solution, obtain pending
Mixed liquor, including：
Solvable barium salt is dissolved in the carbon nanodot solution, the carbon that obtaining carbon nano dot surface-assembled has barium ions is received
Nanodot solutions；
Solvable sulfate is dissolved in into the carbon nano dot surface-assembled has in the carbon nanodot solution of barium ions, with table
The carbon nano dot surface that face is assembled with barium ions forms barium sulfate, obtains the pending mixed liquor.
Preferably, the solvable barium salt is barium chloride or barium nitrate；
The solvable sulfate is potassium sulfate or sodium sulphate or magnesium sulfate.
Preferably, the solvable sulfate is sodium sulphate；
The solvable barium salt is barium chloride；
The mass ratio of solute and barium chloride and sodium sulphate is the first preset value in the carbon nanodot solution:1.7:1, its
In, the span of first preset value is 4.2 × 10-4-1×10-1, including endpoint value.
Preferably, the concentration of the carbon nanodot solution is not more than 2.5mg/mL.
Preferably, extraction process is carried out to the pending mixed liquor, obtaining carbon nano-point phosphor includes：
The pending mixed liquor is centrifuged successively, washed, dried, grinding operation, obtains carbon nano-point phosphor.
A kind of carbon nano-point phosphor, is made using the method described in any of the above-described embodiment.
A kind of LED lamp pearl, including：
LED chip；
Wrap up the encapsulating material of the LED chip；
The carbon nano-point phosphor as described in above-mentioned embodiment is mixed with the encapsulating material.
Preferably, the encapsulating material is the prepolymer for the dimethyl silicone polymer for being mixed with the carbon nano-point phosphor.
Preferably, the mass ratio of the prepolymer of the carbon nano-point phosphor and dimethyl silicone polymer is second default
Value:1；
The span of second preset value is 0.1-3, including endpoint value.
It can be seen from the above technical proposal that the embodiments of the invention provide a kind of carbon nano-point phosphor, preparation method
And LED lamp bead, wherein, the carbon nano-point phosphor preparation method in carbon nanodot solution by adding solvable barium salt and can
Carbon nano dot surface of the mode of molten sulfate in the carbon nanodot solution forms stable barium sulfate.The barium sulfate exists
The pending mixed liquor is carried out to play a part of isolating the reunion each other of carbon nano dot during extraction process, so that
Fluorescent characteristic will not be lost due to aggregation inducing fluorescent quenching effect by obtaining the carbon nano dot, glimmering to obtain the carbon nano dot
Light powder creates precondition.And due to the preferable stability of barium sulfate and the strong fluorescent properties of carbon nano dot so that described
Carbon nano-point phosphor prepares material as preferable LED lamp bead color conversion layer.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 is a kind of schematic flow sheet for carbon nano-point phosphor preparation method that one embodiment of the application provides；
Fig. 2 is a kind of schematic diagram for carbon nano-point phosphor forming process that one embodiment of the application provides；
Fig. 3 is optics of the carbon nano-point phosphor being prepared in the embodiment of the present application 2 under room light and ultraviolet light
Photo；
Fig. 4 is that the carbon nano-point phosphor being prepared in the embodiment of the present application 3 excites in ultraviolet light, blue light and green glow
Under fluorescent emission picture；
Fig. 5 is the fluorescent emission spectrogram for the carbon nano-point phosphor being prepared in the embodiment of the present application 4；
Fig. 6 be in the embodiment of the present application 5 the carbon nano-point phosphor that is prepared in room light, ultraviolet light, blue light and green
Light excite under optical photograph；
Fig. 7 is that the carbon nano-point phosphor being prepared in the embodiment of the present application 6 is placed on concentrated hydrochloric acid, saturation sodium hydroxide
The optical photograph under room light and ultraviolet light in solution and chloroform solvent；
Fig. 8 is the work photo and luminescent spectrum for the cool white light LED lamp bead that the embodiment of the present application 7 is prepared；
Fig. 9 is the work photo and luminescent spectrum for the white light LEDs lamp bead that the embodiment of the present application 8 is prepared；
Figure 10 is the work photo and luminescent spectrum for the warm white LED lamp bead that the embodiment of the present application 9 is prepared.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
The embodiment of the present application provides a kind of carbon nano-point phosphor preparation method, as shown in figure 1, including：
S101：Obtain carbon nanodot solution.
Can be multiple color in the fluorescence color for the carbon nanodot solution that step S101 is obtained, the carbon nanodot solution
It can also be obtained by other means, the application is not limited this by preparing.
In the preferred embodiment of the application, the fluorescence color of the carbon nanodot solution is preferably green or indigo plant
Color.And the process description that will prepare the carbon nanodot solution of blue-fluorescence is as follows：
A：3g citric acids are dissolved in 20mL ammoniacal liquor, obtain clear solution；
B：The clear solution is subjected to microwave heating treatment 5 minutes, obtains grey black viscous liquid；
C：Deionized water is added in the grey black viscous liquid, with 8000 rpms of centrifugation three times,
Remove larger insoluble carbon nano dot aggregation, obtain the carbon nanodot solution with blue-fluorescence.
The preparation method of the carbon nanodot solution of green fluorescence refers to Chinese patent CN102849722A.The application is herein not
Repeat.But the application is not limited the specific fluorescence color of the carbon nanodot solution, specifically depending on actual conditions.
S102：Solvable barium salt and solvable sulfate are dissolved in the carbon nanodot solution, obtain pending mixed liquor,
Wrapped up by barium sulfate on carbon nano dot surface in the pending mixed liquor.
It should be noted that in step s 102, need to carry out after solvable barium salt is added in the carbon nanodot solution
It is sufficiently stirred so that the solvable barium salt is completely dissolved in the carbon nanodot solution；Likewise, solvable sulfate is added
It is also required to be sufficiently stirred after in the carbon nanodot solution, so that the solvable sulfate is completely dissolved in the carbon nanometer
In point solution.
And the sequencing that the application is added in the carbon nanodot solution to the solvable barium salt and solvable sulfate
Do not limit, first add the solvable barium salt, add the solvable sulfate afterwards or first add the solvable sulfate, then
The solvable barium salt is added, specifically depending on actual conditions.
But in the preferred embodiment of the application, solvable barium salt and solvable sulfate are dissolved in the carbon nano dot
Solution includes：
Solvable barium salt is dissolved in the carbon nanodot solution, the carbon that obtaining carbon nano dot surface-assembled has barium ions is received
Nanodot solutions；
Solvable sulfate is dissolved in into the carbon nano dot surface-assembled has in the carbon nanodot solution of barium ions, with table
The carbon nano dot surface that face is assembled with barium ions forms barium sulfate, obtains the pending mixed liquor.
Inventor only changes the dissolving order of the solvable barium salt and solvable sulfate on the premise of keeping variable constant
Carry out contrast experiment's discovery：First the solvable barium salt is dissolved in the carbon nanodot solution, then by the solvable sulfate
The various aspects of performance (fluorescence intensity, stability etc.) for being dissolved in the carbon nano-point phosphor obtained in the carbon nanodot solution is equal
Better than first the solvable sulfate is dissolved in the carbon nanodot solution, then the solvable barium salt is dissolved in the carbon and received
The carbon nano-point phosphor obtained in nanodot solutions.Because the carbon nano dot in the carbon nanodot solution is typically in negative electricity
Property, both its described carbon nano dot surface had had negative electrical charge, after the solvable barium salt is dissolved in the carbon nanodot solution, table
The barium ions that face carries positive charge is uniformly assembled in carbon nano dot surface in the presence of electrostatic attraction, then by the solvable sulfuric acid
After salt is dissolved in the carbon nanodot solution, surface carry negative electrical charge sulfate ion in the presence of electrostatic attraction with band
The barium ions of positive charge combines, and forms barium sulfate；In this process, the barium sulfate of carbon nano dot surface-assembled is uniform and covers
Completely.And if by the dissolving of the solvable sulfate and solvable barium salt order in turn after, barium ions and sulfate ion meeting
Random incorporation forms barium sulfate, it is impossible to ensures that the barium sulfate covers to the uniform parcel of carbon nano dot, is received forming the carbon
During nanodot fluorescence powder, surface barium sulfate coats infull carbon nano dot and is possible to meeting because aggregation inducing fluorescent quenching is imitated
Answer and lose fluorescent characteristic.
S103：Extraction process is carried out to the pending mixed liquor, obtains carbon nano-point phosphor.
After the carbon nano-point phosphor is obtained, mixed with the prepolymer of dimethyl silicone polymer can be used as it is described
The color conversion layer of LED lamp bead.The mass ratio of the carbon nano-point phosphor and the prepolymer of the dimethyl silicone polymer can
Think the second preset value:1；The span of second preset value is 0.1-3, including endpoint value.
Extraction process is carried out to the pending mixed liquor, carbon nano-point phosphor is obtained and specifically includes：
The pending mixed liquor is centrifuged successively, washed, dried, grinding operation, obtains carbon nano-point phosphor.
Specifically, after the pending mixed liquor is obtained, by the pending mixed liquor with 8000 rpms of speed
Degree carries out the centrifugal treating of 3 minutes, will in the product that centrifugation bottom of the tube obtains after washing and centrifuging three times, be put into baking oven with
Preset temperature is dried and the carbon nano-point phosphor is obtained after grinding.
The span of the preset temperature is 80 DEG C -120 DEG C, including endpoint value.The application is to the preset temperature
Specific value does not limit, specifically depending on actual conditions.
On the basis of above-described embodiment, in another embodiment of the application, the solvable barium salt be barium chloride or
Barium nitrate；
The solvable sulfate is potassium sulfate or sodium sulphate or magnesium sulfate.
The application is not limited the specific species of the solvable barium salt and solvable sulfate, specifically regard actual conditions and
It is fixed.
In the preferred embodiment of the application, the solvable sulfate is preferably sodium sulphate；
The solvable barium salt is preferably barium chloride；
The mass ratio of solute and barium chloride and sodium sulphate is the first preset value in the carbon nanodot solution:1.7:1, its
In, the span of first preset value is 4.2 × 10-4-1×10-1, including endpoint value.With first preset value
The change of specific value, the fluorescent characteristic for obtaining the carbon nano dot also change therewith.The application is to first preset value
Specific value does not limit, specifically depending on actual conditions.
On the basis of above-described embodiment, in the further embodiment of the application, the concentration of the carbon nanodot solution
No more than 2.5mg/mL.
In general the upper limit of concentration of the carbon nanodot solution is 50mg/mL, with the concentration of carbon nanodot solution
Rise, the amount of the carbon nano-point phosphor of acquisition is more.But in reality it was found that, when the carbon nanodot solution
After concentration is more than 2.5mg/mL, add wherein after solvable barium salt can so that the property of the carbon nanodot solution changes,
Precipitation is produced in advance, influences the preparation of the carbon nano-point phosphor.
In order to preferably embody the feasibility of the carbon nano-point phosphor preparation method of the embodiment of the present application offer, under
Face will carry out illustration with multiple embodiments.
Embodiment 1：
In the present embodiment, the green fluorescence carbon nanodot solution 10mL that concentration is 1.0mg/mL is taken, first adds 1.2g's
BaCl2, after stirring 5 minutes, add 0.7g Na2SO4, and continue stirring and obtain the pending mixed liquor.Wait to locate by described
The centrifugation that mixed liquor is carried out 3 minutes with 8000 rpms of speed is managed, centrifugation bottom of the tube products therefrom is through washing and centrifuging three
After secondary, it is put into 100 DEG C of baking ovens, that centrifugation bottom of the tube is collected after drying does not grind fluorescent material, and the fluorescent material that do not grind is entered
The carbon nano-point phosphor is obtained after row grinding.
Fig. 2 is the schematic diagram for the carbon nano-point phosphor forming process that the embodiment of the present application provides, due to carbon nano dot table
Face group carries a large amount of negative electrical charges, it is thus possible to adsorbs a large amount of Ba by electrostatic attraction2+, and therefore form Ba2+The carbon of cladding
Nano dot, the SO then added4 2-Then can be by carbon nano dot surface Ba2+Attracted, final in-situ preparation BaSO4, and then obtain base
In the overstable fluorescent material of carbon nano dot.
Embodiment 2：
The green fluorescence carbon nanodot solution 100mL that concentration is 2.5mg/mL is taken, first adds 24.4g BaCl2, stirring 5
After minute, 14.2g Na is added2SO4, and continue stirring and obtain the pending mixed liquor.By the pending mixed liquor with
8000 rpms of speed carries out the centrifugation of 3 minutes, and centrifugation bottom of the tube products therefrom is put into after washing and centrifuging three times
That centrifugation bottom of the tube is collected in 100 DEG C of baking ovens, after drying does not grind fluorescent material, and described do not grind after fluorescent material is ground is obtained
Obtain the carbon nano-point phosphor.
Fig. 3 is the carbon nano-point phosphor being prepared in example 2 in room light Fig. 3 (a) and ultraviolet light Fig. 3
(b) optical photograph under, from figure 3, it can be seen that can be obtained within a very short time largely using the technology proposed in the present invention
Carbon nano-point phosphor, as shown in Fig. 3 (a), and under ultraviolet light, the carbon nano-point phosphor has bright indigo plant
Green fluorescence, as shown in Fig. 3 (b).
Embodiment 3：
The green fluorescence carbon nanodot solution 10mL that concentration is 2.5mg/mL is taken, first adds 2.4g BaCl2, stir 5 points
Zhong Hou, add 1.4g Na2SO4, and continue stirring and obtain the pending mixed liquor.By the pending mixed liquor with
8000 rpms of speed carries out the centrifugation of 3 minutes, and centrifugation bottom of the tube products therefrom is put into after washing and centrifuging three times
That centrifugation bottom of the tube is collected in 100 DEG C of baking ovens, after drying does not grind fluorescent material, and described do not grind after fluorescent material is ground is obtained
Obtain the carbon nano-point phosphor.
Fig. 4 is that the carbon nano-point phosphor that the embodiment of the present application 3 is prepared swashs in ultraviolet light, blue light and green glow
The fluorescent emission picture given, institute is excited with different exciting lights, such as ultraviolet light, blue light and green glow from fig. 4, it can be seen that working as
When stating carbon nano-point phosphor, the blue green light Fig. 4 (a) for coming from the full surface of fluorescent material particulate, green-yellow light Fig. 4 can be observed
(b) and feux rouges Fig. 4 (c) launches, i.e., the fluorescent material shows the characteristics of luminescence that obvious excitation wavelength relies on, while also illustrates
Carbon nano dot is uniformly coated on inside fluorescent material.
Embodiment 4：
The green fluorescence carbon nanodot solution 10mL that concentration is 2.5mg/mL is taken, first adds 0.8g BaCl2, stir 5 points
Zhong Hou, add 0.4g Na2SO4, and continue stirring and obtain the pending mixed liquor.By the pending mixed liquor with
8000 rpms of speed carries out the centrifugation of 3 minutes, and centrifugation bottom of the tube products therefrom is put into after washing and centrifuging three times
That centrifugation bottom of the tube is collected in 100 DEG C of baking ovens, after drying does not grind fluorescent material, and described do not grind after fluorescent material is ground is obtained
Obtain the carbon nano-point phosphor.
Fig. 5 is the fluorescent emission spectrogram of carbon nano-point phosphor that the embodiment of the present invention 4 is prepared, can be with from Fig. 5
Find out, under the exciting of 405nm light, its fluorescence emission wavelengths is 520nm, this photoluminescent property with initial carbon nanodot solution
It is consistent.In addition, the quantum efficiency of fluorescent material is measured as 27%, this numerical value is higher than the quantum efficiency of carbon nanodot solution
(17%), illustrate that the carbon nano-point phosphor is expected in the color conversion layer material applied to LED lamp bead.
Embodiment 5：
The blue-fluorescence carbon nanodot solution 50mL that concentration is 1.0mg/mL is taken, first adds 12.2g BaCl2, stir 5 points
Zhong Hou, add 7.1g Na2SO4, and continue stirring and obtain reaction mixture.By gained mixed liquor with 8000 rpms
Speed carries out the centrifugation of 3 minutes, and centrifugation bottom of the tube products therefrom is put into 100 DEG C of baking ovens after washing and centrifuging three times, dried
Centrifugation bottom of the tube is collected afterwards and does not grind fluorescent material, does not grind that to obtain the carbon nano dot after fluorescent material is ground glimmering to described
Light powder.
Fig. 6 is the carbon nano-point phosphor being prepared in the embodiment of the present application 5 in room light Fig. 6 (a), ultraviolet light Fig. 6
(b) optical photograph under, blue light Fig. 6 (c) and green glow Fig. 6 (d) is excited, from fig. 6, it can be seen that proposition prepares carbon in the present invention
The method of nano-point phosphor can also be applied to prepare the negatively charged blue-light carbon nano dot in surface, thus methods described have it is general
Adaptive.Meanwhile when exciting the fluorescent material with different exciting lights, such as ultraviolet light, blue light and green glow, it can observe and come from
Blue light Fig. 6 (b), green-yellow light Fig. 6 (c) and feux rouges Fig. 6 (d) in the full surface of carbon nano-point phosphor particulate launch, i.e., this is glimmering
Light powder shows the characteristics of luminescence that obvious excitation wavelength relies on, while also illustrates that blue-light carbon nano dot is uniformly coated on sulphur
Inside sour barium.
Embodiment 6：
The green fluorescence carbon nanodot solution 10mL that concentration is 0.5mg/mL is taken, first adds 2.4g BaCl2, stir 5 points
Zhong Hou, add 1.4g Na2SO4, and continue stirring and obtain the pending mixed liquor.By the pending mixed liquor with
8000 rpms of speed carries out the centrifugation of 3 minutes, and centrifugation bottom of the tube products therefrom is put into after washing and centrifuging three times
That centrifugation bottom of the tube is collected in 100 DEG C of baking ovens, after drying does not grind fluorescent material, and described do not grind after fluorescent material is ground is obtained
Obtain the carbon nano-point phosphor.Then it is molten fluorescent material to be respectively placed in concentrated hydrochloric acid, saturation sodium hydroxide solution and chloroform
In agent.
Fig. 7 is that the carbon nano-point phosphor that the embodiment of the present invention 6 is prepared is placed on concentrated hydrochloric acid Fig. 7 (a) and Fig. 7 (d),
Room light Fig. 7 (a-c) and purple in saturation sodium hydroxide solution Fig. 7 (b) and Fig. 7 (e) and chloroform solvent Fig. 7 (c) and Fig. 7 (f)
Optical photograph under outer smooth Fig. 7 (d-f), from figure 7 it can be seen that fluorescent material can be stable in the presence of various strong acid, strong base solution
And in organic solvent.
Accordingly, the embodiment of the present application additionally provides a kind of carbon nano-point phosphor, and the carbon nano-point phosphor uses
Method described in any of the above-described embodiment is made.
Accordingly, the embodiment of the present application additionally provides a kind of LED lamp pearl, including：
LED chip；
Wrap up the encapsulating material of the LED chip；
The carbon nano-point phosphor as described in above-mentioned embodiment is mixed with the encapsulating material.
On the basis of above-described embodiment, in one embodiment of the application, the encapsulating material is to be mixed with the carbon
The prepolymer of the dimethyl silicone polymer of nano-point phosphor.
On the basis of above-described embodiment, in another embodiment of the application, the carbon nano-point phosphor is with gathering
The mass ratio of the prepolymer of dimethyl siloxane is the second preset value:1；
The span of second preset value is 0.1-3, including endpoint value.With the specific value of the second preset value
Change, International Commission on Illumination (the Commission Internationale de L ' for the light that the LED lamp bead is sent
Eclairage, CIE) coordinate and colour temperature can change therewith.The application is not limited the specific value of second preset value
It is fixed, specifically depending on actual conditions.
The carbon nano-point phosphor applied to the LED lamp bead and the LED will be illustrated with multiple embodiments below
The Making programme of pearl, and test the optical property of the LED lamp bead.
Embodiment 7：
The green fluorescence carbon nanodot solution 10mL that concentration is 0.1mg/mL is taken, first adds 2.4g BaCl2, stir 5 points
Zhong Hou, add 1.4g Na2SO4, and continue stirring and obtain the pending mixed liquor.By the pending mixed liquor with
8000 rpms of speed carries out the centrifugation of 3 minutes, and centrifugation bottom of the tube products therefrom is put into after washing and centrifuging three times
That centrifugation bottom of the tube is collected in 100 DEG C of baking ovens, after drying does not grind fluorescent material, and described do not grind after fluorescent material is ground is obtained
Obtain the carbon nano-point phosphor.The prepolymer of ground carbon nano-point phosphor and dimethyl silicone polymer is taken according to quality
Than for 0.1：1 is blended, and is then coated with unencapsulated LED chip, then be positioned over certain temperature (can be at 80 DEG C -120 DEG C
Between value) baking oven in, (depending on oven temperature, when oven temperature is 80 DEG C, required time is 3 small after certain time
When), that is, obtain packaged light as the LED lamp bead of cool white light.
What Fig. 8 was that the embodiment of the present invention 7 is prepared is color conversion layer material using the carbon nano-point phosphor
The work photo and luminescent spectrum of cool white light LED lamp bead, it can be seen that the carbon nano-point phosphor can conduct
LED color changes layer material, and realizes cool white light LED lamp bead, and its CIE coordinate is (0.28,0.32), colour temperature 8520K.
Embodiment 8：
The green fluorescence carbon nanodot solution 10mL that concentration is 1.0mg/mL is taken, successively adds 2.4g BaCl2, stirring 5
After minute, 1.4g Na is added2SO4, and continue stirring and obtain the pending mixed liquor.By the pending mixed liquor with
8000 rpms of speed carries out the centrifugation of 3 minutes, and centrifugation bottom of the tube products therefrom is put into after washing and centrifuging three times
That centrifugation bottom of the tube is collected in 100 DEG C of baking ovens, after drying does not grind fluorescent material, and described do not grind after fluorescent material is ground is obtained
Obtain the carbon nano-point phosphor.The prepolymer of ground carbon nano-point phosphor and dimethyl silicone polymer is taken according to quality
Than for 2：1 is blended, and is then coated with unencapsulated LED chip, then is positioned in 80 DEG C of baking ovens, after 3 hours, that is, is obtained
Packaged lights as the LED lamp bead of white light.
What Fig. 9 was that the embodiment of the present invention 8 is prepared is color conversion layer material using the carbon nano-point phosphor
The work photo and luminescent spectrum of white light LEDs lamp bead, it can be seen that the carbon nano-point phosphor can conduct
LED color changes layer material, and realizes white light LEDs lamp bead, and its CIE coordinate is (0.34,0.38), colour temperature 5237K.
Embodiment 9：
The green fluorescence carbon nanodot solution 10mL that concentration is 2.5mg/mL is taken, successively adds 2.4g BaCl2, stirring 5
After minute, 1.4g Na is added2SO4, and continue stirring and obtain the pending mixed liquor.By the pending mixed liquor with
8000 rpms of speed carries out the centrifugation of 3 minutes, and centrifugation bottom of the tube products therefrom is put into after washing and centrifuging three times
That centrifugation bottom of the tube is collected in 100 DEG C of baking ovens, after drying does not grind fluorescent material, and described do not grind after fluorescent material is ground is obtained
Obtain the carbon nano-point phosphor.The prepolymer of ground carbon nano-point phosphor and dimethyl silicone polymer is taken according to quality
Than for 3：1 is blended, and is then coated with unencapsulated LED chip, then is positioned in 80 DEG C of baking ovens, after 3 hours, that is, is obtained
Packaged lights as the LED lamp bead of warm white.
Figure 10 be the embodiment of the present invention 9 be prepared utilize the warm white that the carbon nano-point phosphor is color conversion layer
The work photo and luminescent spectrum of light LED lamp bead, it can be seen that the carbon nano-point phosphor can be used as LED
Color conversion layer material, and realize warm white LED lamp bead, its CIE coordinate are (0.45,0.50), colour temperature 3483K.
In summary, the embodiment of the present application provides a kind of carbon nano-point phosphor, preparation method and LED lamp bead, wherein,
The carbon nano-point phosphor preparation method in carbon nanodot solution by way of adding solvable barium salt and solvable sulfate
Carbon nano dot surface-assembled barium ions and sulfate ion in the carbon nanodot solution, so as to molten in the carbon nano dot
Carbon nano dot surface in liquid forms stable barium sulfate.The barium sulfate is carrying out extraction process to the pending mixed liquor
During play a part of isolating carbon nano dot and reunite each other so that the carbon nano dot will not be due to aggregation inducing
Fluorescent quenching effect and lose fluorescent characteristic, create precondition to obtain the carbon nano-point phosphor.And due to sulfuric acid
The strong fluorescent properties of the preferable stability of barium and carbon nano dot so that the carbon nano-point phosphor turns into preferable LED
The color conversion layer of pearl prepares material.
Each embodiment is described by the way of progressive in this specification, what each embodiment stressed be and other
The difference of embodiment, between each embodiment identical similar portion mutually referring to.
The foregoing description of the disclosed embodiments, professional and technical personnel in the field are enable to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (9)
- A kind of 1. carbon nano-point phosphor preparation method, it is characterised in that including：Obtain carbon nanodot solution；Solvable barium salt and solvable sulfate are dissolved in the carbon nanodot solution, obtain pending mixed liquor, it is described to wait to locate Wrapped up by barium sulfate on carbon nano dot surface in reason mixed liquor；Extraction process is carried out to the pending mixed liquor, obtains carbon nano-point phosphor；It is described that solvable barium salt and solvable sulfate are dissolved in the carbon nanodot solution, pending mixed liquor is obtained, including：Solvable barium salt is dissolved in the carbon nanodot solution, obtaining carbon nano dot surface-assembled has the carbon nano dot of barium ions Solution；Solvable sulfate is dissolved in into the carbon nano dot surface-assembled has in the carbon nanodot solution of barium ions, with surface group Carbon nano dot surface equipped with barium ions forms barium sulfate, obtains the pending mixed liquor.
- 2. according to the method for claim 1, it is characterised in that the solvable barium salt is barium chloride or barium nitrate；The solvable sulfate is potassium sulfate or sodium sulphate or magnesium sulfate.
- 3. according to the method for claim 2, it is characterised in that the solvable sulfate is sodium sulphate；The solvable barium salt is barium chloride；The mass ratio of solute and barium chloride and sodium sulphate is the first preset value in the carbon nanodot solution:1.7:1, wherein, institute The span for stating the first preset value is 4.2 × 10-4-1×10-1, including endpoint value.
- 4. according to the method for claim 1, it is characterised in that the concentration of the carbon nanodot solution is not more than 2.5mg/ mL。
- 5. according to the method for claim 1, it is characterised in that extraction process is carried out to the pending mixed liquor, obtained Carbon nano-point phosphor includes：The pending mixed liquor is centrifuged successively, washed, dried, grinding operation, obtains carbon nano-point phosphor.
- 6. a kind of carbon nano-point phosphor, it is characterised in that be made using the method described in claim any one of 1-5.
- A kind of 7. LED lamp pearl, it is characterised in that including：LED chip；Wrap up the encapsulating material of the LED chip；Carbon nano-point phosphor as claimed in claim 6 is mixed with the encapsulating material.
- 8. LED lamp bead according to claim 7, it is characterised in that the encapsulating material is glimmering to be mixed with the carbon nano dot The prepolymer of the dimethyl silicone polymer of light powder.
- 9. LED lamp bead according to claim 8, it is characterised in that the carbon nano-point phosphor and polydimethylsiloxanes The mass ratio of the prepolymer of alkane is the second preset value:1；The span of second preset value is 0.1-3, including endpoint value.
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