CN108587614B - Pure carbon nanodot, preparation method thereof and LED light source - Google Patents
Pure carbon nanodot, preparation method thereof and LED light source Download PDFInfo
- Publication number
- CN108587614B CN108587614B CN201810266517.3A CN201810266517A CN108587614B CN 108587614 B CN108587614 B CN 108587614B CN 201810266517 A CN201810266517 A CN 201810266517A CN 108587614 B CN108587614 B CN 108587614B
- Authority
- CN
- China
- Prior art keywords
- pure carbon
- nanodot
- carbon
- carbon nanodot
- nanodots
- 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.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 120
- 239000002096 quantum dot Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 26
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 26
- -1 amino compound Chemical class 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 28
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000004202 carbamide Substances 0.000 claims description 13
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 7
- 229910001626 barium chloride Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 5
- 229930091371 Fructose Natural products 0.000 claims description 5
- 239000005715 Fructose Substances 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 229960001484 edetic acid Drugs 0.000 claims 1
- 238000010923 batch production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 9
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013080 microcrystalline material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002520 smart material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Images
Classifications
-
- 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
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Biophysics (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a pure carbon nanodot, a preparation method thereof and an LED light source. The invention discloses a preparation method of pure carbon nanodots, which comprises the following steps: adding inorganic salt, polyhydroxy compound and amino compound into deionized water, dissolving, and heating in vacuum to obtain pure carbon nanodots; the mass ratio of the inorganic salt polyhydroxy compound to the amino compound is 0.1-2: 0.1-5: 1. the technical scheme disclosed by the invention is simple and convenient in experimental operation, low in risk, good in experimental repeatability, capable of realizing batch production and high in luminous intensity of the obtained carbon nanodots.
Description
Technical Field
The invention relates to the technical field of carbon nanodots, in particular to a pure carbon nanodot with high-efficiency luminescence, a preparation method thereof and an LED light source.
Background
Carbon nanodots are a novel fluorescent substance based on carbon materials, which have many advantages, such as low preparation cost, high fluorescence quantum efficiency, low biotoxicity, etc., and are further applied in various fields, such as smart materials, photovoltaic and optoelectronic devices, sensors, bioluminescent markers, etc., and thus are gradually becoming a material with great application prospects.
In the prior art, carbon nanodots may be prepared by various methods, such as laser ablation, electrochemical methods, arc discharge, pyrolysis, ultrasound, and microwave methods. However, the sizes of the carbon nanodots prepared by the methods are difficult to be uniform, and the carbon nanodots with different particle diameters usually have different band gaps, so that the fluorescence quenching is caused by energy transfer among different energy levels when the prepared carbon nanodots are in an aggregation state. The high-brightness carbon nano-dot solid film and the bulk phase material can not be realized, and the application of the carbon nano-dot material in a solid luminescent system is greatly limited.
The prior art discloses a preparation method of a carbon nano-dot doped sodium chloride microcrystalline material, which comprises the following steps: 1) adding sufficient sodium chloride crystals into the green light emitting carbon nano-dot solution, heating and stirring to prepare a sodium chloride saturated solution of the green light emitting carbon nano-dots; 2) and the obtained saturated solution is easily cooled, purified, dried and ground to obtain the carbon nano-dot sodium chloride-doped microcrystalline material. The preparation method of the green light emitting carbon nano-dot solution comprises the following steps: 11) mixing and dissolving a preset amount of citric acid and urea in deionized water to obtain a colorless and transparent solution; 12) heating the colorless and transparent solution for a preset time to obtain a tan viscous liquid; 13) and drying the viscous liquid, putting the solution in deionized water, and then carrying out centrifugal treatment to remove insoluble carbon nano-dot particles so as to obtain the carbon nano-dots emitting green light. The carbon nano-dots obtained by the method have low fluorescence quantum efficiency in a solution and have serious aggregation-induced fluorescence quenching phenomenon, so that the pure carbon nano-dots high-efficiency luminescent thin film and solid materials cannot be prepared.
In the prior art, a nitrogen, sulfur and copper co-doped carbon nanodot is prepared by a microwave method or by a microwave method after silane surface modification by using an organic compound containing polycarboxyl or polyhydroxy as a carbon source, an amino compound as a nitrogen source, a compound containing sulfur as a sulfur source and a cuprous compound as a copper source; the grain diameter of the carbon nano-dots is 8nm-15 nm. The carbon nanodots have poor water solubility, can only exist in a powdery form, and cannot be prepared into a high-efficiency transparent luminescent film, so that the further application of the carbon nanodots is limited.
The prior art discloses a carbon nanodot which is prepared by taking an organic compound containing polycarboxyl or polyhydroxy as a raw material, or taking amino acid as a raw material and taking urea as a surface passivator, and comprises the following steps: preparing aqueous solution from urea and an organic compound containing polycarboxyl or polyhydroxy or amino acid according to the mass ratio of 0.1:1-4: 1; secondly, performing microwave heating reaction on the prepared aqueous solution to obtain a brownish black solid; thirdly, the obtained brown black solid is heated in vacuum to remove residual micromolecular compounds, and then the carbon nanodots are obtained; the carbon nanodot surface has an amide group and a carboxyl group. However, since uniform heating cannot be achieved in the microwave heating process, a locally too high heating temperature causes excessive carbonization, resulting in formation of a poorly soluble matt material, and a locally too low temperature causes incomplete carbonization, resulting in failure to form carbon nanodots. Finally, the carbon nano-dots are not uniform in size, energy transfer exists in a solid state, and further aggregation-induced fluorescence quenching exists, so that efficient solid-state light emission is difficult to realize.
Disclosure of Invention
In view of the above, the present invention provides a pure carbon nanodot with efficient light emission, a method for preparing the same, and an application of the pure carbon nanodot in laser.
In a first aspect, the present invention provides a method for preparing pure carbon nanodots, comprising the steps of: adding inorganic salt, polyhydroxy compound and amino compound into deionized water, dissolving, and heating in vacuum to obtain pure carbon nanodots; the mass ratio of the inorganic salt polyhydroxy compound to the amino compound is (0.1-2): (0.1-5): 1.
alternatively, in some embodiments, the method of preparation comprises the steps of: adding inorganic salt, polyhydroxy compound and amino compound into deionized water, fully dissolving, drying, and heating in vacuum to obtain pure carbon nanodots.
Alternatively, in some embodiments, the mass ratio of the inorganic salt, the polyhydroxy compound, and the amino compound is (0.5-1.5): (0.5-3): 1, more preferably (0.5-1.5): 0.5: 1.
optionally, in some embodiments, the inorganic salt is selected from one or more of calcium chloride, barium chloride, magnesium chloride.
Optionally, in some embodiments, the polyol is selected from one or more of citric acid, glucose, sucrose, fructose, ethylenediaminetetraacetic acid, glycerol, chitosan, tartaric acid, oxalic acid, or starch; the amino compound is selected from one of urea, ethylenediamine or ammonia water.
Optionally, in some embodiments, the drying is drying at atmospheric pressure; the vacuum heating is carried out for 0.8h-1.5h at the temperature of 100-300 ℃ in a vacuum state.
Optionally, in some embodiments, the product with strong fluorescence is obtained after vacuum heating, and then is dialyzed by acidification.
In a second aspect, the present invention also provides a pure carbon nanodot prepared by the method of the present invention, wherein the pure carbon nanodot is a spherical nanoparticle, and the average particle size of the pure carbon nanodot is 2nm to 6 nm.
Alternatively, in some embodiments, the ultraviolet absorption peak of the pure carbon nanodots is between 330nm and 410nm, and the fluorescence emission peak of the aqueous solution of the pure carbon nanodots is between 450nm and 535 nm.
In a third aspect, the invention also provides an LED light source prepared by the following method: the pure carbon nano-dots provided by the invention are mixed with polydimethylsiloxane according to the mass ratio (0.1-8) of 1, then the mixture is coated on an unpackaged LED, and the LED light source is dried, so that the packed LED light source is obtained.
The raw materials adopted by the invention are all commercially available raw materials, further processing is not needed, the raw materials are directly mixed according to a certain proportion and the carbon nanodots can be prepared by a vacuum heating one-step method, so that the experimental operation is simple and convenient, the risk is low, the experimental repeatability is good, the mass production can be realized, and the luminous intensity of the obtained carbon nanodots is high.
Drawings
Fig. 1A is a room light photograph of a carbon nanodot product prepared according to example 1 of the present invention;
fig. 1B is a fluorescent photograph of a carbon nanodot product prepared according to example 1 of the present invention;
fig. 1C is a TEM transmission photograph of a carbon nanodot product prepared according to example 1 of the present invention;
FIG. 2A is a UV-VIS absorption spectrum of a carbon nanodot product prepared according to example 2 of the present invention after being dissolved in water;
FIG. 2B is a fluorescence emission spectrum of a carbon nanodot product prepared according to example 2 of the present invention after being dissolved in water;
FIG. 3 is a photograph of a white light emitting diode prepared from a pure carbon nanodot product according to example 3 of the present invention;
fig. 4 is a fluorescence emission spectrum of a carbon nanodot product prepared according to example 5 of the present invention under ultraviolet light excitation;
fig. 5 is a fluorescence emission spectrum of a carbon nanodot product prepared according to example 6 of the present invention under ultraviolet light excitation;
fig. 6 is a fluorescence emission spectrum of a carbon nanodot product prepared according to example 7 of the present invention under uv light excitation.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terms "first," "second," "third," "fourth," and the like in the description and in the claims, as well as in the drawings, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It will be appreciated that the data so used may be interchanged under appropriate circumstances such that the embodiments described herein may be practiced otherwise than as specifically illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of a pure carbon nanodot, a pure carbon nanodot and an LED light source.
In a first aspect, the present invention provides a method for preparing pure carbon nanodots, comprising the steps of: adding inorganic salt, polyhydroxy compound and amino compound into deionized water, dissolving, and heating in vacuum to obtain pure carbon nanodots; the mass ratio of the inorganic salt polyhydroxy compound to the amino compound is 0.1-2: 0.1-5: 1.
in some specific embodiments, the preparation method comprises the steps of: adding inorganic salt, polyhydroxy compound and amino compound into deionized water, fully dissolving, drying, and heating in vacuum to obtain pure carbon nanodots.
In some specific embodiments, the mass ratio of the inorganic salt, the polyhydroxy compound, and the amino compound is 0.5 to 1.5: 0.5-3: 1, more preferably 0.5 to 1.5: 0.5: 1.
in some specific embodiments, the inorganic salt is selected from one or more of calcium chloride, barium chloride, magnesium chloride.
In some specific embodiments, the polyol is selected from one or more of citric acid, glucose, sucrose, fructose, ethylenediaminetetraacetic acid, glycerol, chitosan, tartaric acid, oxalic acid, or starch.
In some specific embodiments, the drying is drying at atmospheric pressure; the vacuum heating is carried out for 0.8h-1.5h at the temperature of 100-300 ℃ in a vacuum state.
In some embodiments, the product with strong fluorescence is obtained after vacuum heating, and then is dialyzed by acidification.
In a second aspect, the present invention also provides a pure carbon nanodot, which is prepared by the method for preparing a pure carbon nanodot provided by the present invention, wherein the pure carbon nanodot is a spherical nanoparticle, the pure carbon nanodot overcomes aggregation-induced fluorescence quenching, and the average particle size of the pure carbon nanodot is 2nm to 6 nm.
In some specific embodiments, the ultraviolet absorption peak of the pure carbon nanodots is between 330nm and 410nm, and the fluorescence emission peak of the aqueous solution of the pure carbon nanodots is between 450nm and 535 nm.
In a third aspect, the invention also provides an LED light source prepared by the following method: and (3) blending the pure carbon nano-dots and polydimethylsiloxane according to the mass ratio of 0.1-8:1, then coating the mixture on an unpackaged LED, and drying to obtain the packaged LED light source.
The raw materials adopted by the invention are all commercially available raw materials, further processing is not needed, the raw materials are directly mixed according to a certain proportion and the carbon nanodots can be prepared by a vacuum heating one-step method, so that the experimental operation is simple and convenient, the risk is low, the experimental repeatability is good, the mass production can be realized, and the luminous intensity of the obtained carbon nanodots is high.
The present invention may be further understood by the following preferred specific examples of the invention, which are set forth to provide a clear understanding to those of ordinary skill in the art and are not intended to be limiting of the invention. Insubstantial modifications and adaptations of the invention as described above will now occur to those skilled in the art and are intended to be within the scope of the invention.
Example 1
Dissolving 0.5g of anhydrous calcium chloride powder, 0.5g of citric acid and 1g of urea in deionized water, drying at normal pressure after fully dissolving, and heating at 250 ℃ for one hour in a vacuum state to obtain a carbon nanodot product D1.
Fig. 1A is a room light photograph, fig. 1B is a fluorescence photograph, and fig. 1C is a TEM transmission photograph of the carbon nanodot product of example 1 according to the present invention. As can be seen from fig. 1A and 1B, the prepared carbon nanodot product D1 appeared as a swelled sphere and had bright yellow-green fluorescence. As can be calculated from fig. 1C, the prepared carbon nanodots are spherical nanoparticles with a particle size of about 4 nm.
Example 2
Dissolving 0.8g of anhydrous calcium chloride powder, 0.5g of citric acid and 1g of urea in deionized water, drying at normal pressure after full dissolution, heating at 250 ℃ for one hour in a vacuum state to obtain a carbon nanodot product, and dissolving the carbon nanodot product in deionized water to obtain a carbon nanodot product D2.
Fig. 2A is an ultraviolet-visible absorption spectrum of the carbon nanodot product D2 dissolved in deionized water according to example 2 of the present invention, and fig. 2B is a fluorescence emission spectrum of the carbon nanodot product D2 dissolved in deionized water according to example 2 of the present invention. As can be seen from fig. 2A, the uv absorption peaks of the prepared carbon nanodots D2 are at 330 and 406 nm. As can be seen from FIG. 2B, the fluorescence emission peak of the carbon nanodot aqueous solution was at 520nm, with green fluorescence.
Example 3
Dissolving 1g of anhydrous calcium chloride powder, 0.5g of citric acid and 1g of urea in deionized water, drying the mixture at normal pressure after the mixture is fully dissolved, and heating the mixture for one hour at 250 ℃ in a vacuum state to obtain a carbon nanodot product D3. Taking the ground carbon nanodot product and polydimethylsiloxane according to the mass ratio of 1:1, then coating the mixture on an unpackaged LED, and then placing the mixture in an oven at 80 ℃ for 3 hours to obtain the packaged LED light source emitting white light.
FIG. 3 shows a white LED light source prepared in example 3 of the present invention, which has CIE coordinates (0.33, 0.34) and a color temperature of 5603K.
Example 4
Dissolving 1.5g of anhydrous calcium chloride powder, 0.5g of citric acid and 1g of urea in deionized water, drying at normal pressure after full dissolution, heating at 250 ℃ for one hour in a vacuum state to obtain a carbon nanodot product D4, dissolving the carbon nanodot product D4 in a dilute hydrochloric acid solution, and removing small molecular substances by a dialysis method.
Example 5
Dissolving 0.5g of anhydrous calcium chloride powder, 1g of citric acid and 1g of urea in deionized water, drying at normal pressure after fully dissolving, and heating at 140 ℃ for one hour in a vacuum state to obtain a carbon nanodot product D5.
Fig. 4 is a fluorescence emission spectrum of the carbon nanodot product D5 under ultraviolet light excitation according to example 5 of the present invention. As can be seen from fig. 4, the prepared carbon nanodot product has a fluorescence emission peak at 450nm with blue fluorescence.
Example 6
Dissolving 0.5g of anhydrous calcium chloride powder, 1g of citric acid and 1g of urea in deionized water, drying at normal pressure after fully dissolving, and heating at 160 ℃ for one hour in a vacuum state to obtain a carbon nanodot product D6.
Fig. 5 is a fluorescence emission spectrum of the carbon nanodot product of example 6 of the present invention under uv excitation. As can be seen from fig. 5, the prepared carbon nanodot product has a fluorescence emission peak at 500nm and has blue-green fluorescence.
Example 7
Dissolving 0.5g of anhydrous calcium chloride powder, 1g of citric acid and 1g of urea in deionized water, drying at normal pressure after fully dissolving, and heating at 200 ℃ for one hour in a vacuum state to obtain a carbon nanodot product D7.
Fig. 6 is a fluorescence emission spectrum of the carbon nanodot product D7 under ultraviolet light excitation according to example 7 of the present invention. As can be seen from fig. 6, the prepared carbon nanodot product has a fluorescence emission peak at 520nm, with green fluorescence.
Example 8
1.5g of barium chloride, 0.5g of glucose and 1g of ethylenediamine are dissolved in deionized water, and after the barium chloride, the glucose and the ethylenediamine are fully dissolved, the barium chloride, the glucose and the ethylenediamine are dried under normal pressure, and then the barium chloride, the glucose and the ethylenediamine are heated for one hour under a vacuum state, so that the carbon nanodot D8 is obtained.
Example 9
1.5g of magnesium chloride, 2g of sucrose and 1g of ammonia water are dissolved in deionized water, and after the magnesium chloride, the sucrose and the ammonia water are fully dissolved, the mixture is dried under normal pressure and then heated for two hours in a vacuum state, so that the carbon nanodot D9 is obtained.
Example 10
0.5g of magnesium chloride, 2g of glucose and 1g of ethylenediamine are dissolved in deionized water, and after the magnesium chloride, the glucose and the ethylenediamine are fully dissolved, the mixture is dried under normal pressure and then heated for two hours under a vacuum state, so that the carbon nanodot D10 is obtained.
Example 11
0.5g of magnesium chloride, 3g of fructose and 1g of ammonia water are dissolved in deionized water, and after the magnesium chloride, the fructose and the ammonia water are fully dissolved, the solution is dried under normal pressure, and then the solution is heated for two hours under a vacuum state, so that the carbon nanodot D11 is obtained.
Example 12
0.1g of magnesium chloride, 0.1g of glycerol and 1g of ammonia water are dissolved in deionized water, and after the magnesium chloride, the glycerol and the ammonia water are fully dissolved, the solution is dried under normal pressure and then heated for two hours under a vacuum state, so that the carbon nanodot D12 is obtained.
Example 13
2g of magnesium chloride, 5g of glycerol and 1g of ammonia water are dissolved in deionized water, and after the magnesium chloride, the glycerol and the ammonia water are fully dissolved, the solution is dried under normal pressure and then heated for two hours under a vacuum state, so that the carbon nanodot D13 is obtained.
Comparative example 1
Mixing 3g of citric acid and 6g of urea, and dissolving in 20ml of deionized water to obtain a colorless and transparent solution; heating the obtained colorless transparent solution with microwave for about 5min to obtain brown viscous liquid; and drying the obtained viscous liquid, dissolving the viscous liquid in deionized water, centrifuging for 3 times at 8000 rpm, and removing insoluble carbon nanodot particles to obtain carbon nanodot DS1 emitting green light.
Comparative example 2
Carbon nanodots DS2 were prepared as in CN106566540A example 1.
In summary, in the embodiments 1 to 13 of the present invention, the preparation method of vacuum high temperature foaming is applied to the luminescent color conversion layer material and the laser device, and the method can cause the reaction raw material to be carbonized in the formed material in a limited domain by adjusting the reaction conditions, so as to obtain a large amount of high brightness fluorescent carbon nanodots. The preparation method can obtain a large number of carbon nano-dots with high fluorescence quantum efficiency and uniform size by adjusting the reaction temperature.
The carbon nanodots obtained in the comparative examples 1-2 have low fluorescence quantum efficiency in the solution and have severe aggregation-induced fluorescence quenching phenomenon, so that the pure carbon nanodot high-efficiency luminescent thin film and solid material cannot be prepared; the spot water solubility is poor, and the spot water solubility only exists in a powdery form, so that the spot water solubility cannot be prepared into a high-efficiency transparent luminescent film, and further the further application of the spot water solubility is limited.
While the above method for preparing pure carbon nanodots provided by the present invention has been described in detail, those skilled in the art may change the concept of the embodiments of the present invention in terms of the specific implementation and application scope, and in summary, the content of the present disclosure should not be construed as limiting the present invention.
Claims (6)
1. A method for preparing pure carbon nanodots is characterized by comprising the following steps: adding inorganic salt, polyhydroxy compound and amino compound into deionized water, drying after fully dissolving, and then heating in vacuum to obtain pure carbon nanodots; the mass ratio of the inorganic salt to the polyhydroxy compound to the amino compound is 0.1-2: 0.1-5: 1;
the drying is drying under normal pressure; the vacuum heating is carried out for 0.8h to 1.5h at the temperature of 100 ℃ to 300 ℃ in a vacuum state;
the inorganic salt is selected from one or more of calcium chloride, barium chloride and magnesium chloride;
the polyhydroxy compound is selected from one or more of citric acid, glucose, sucrose, fructose, ethylene diamine tetraacetic acid, glycerol, chitosan, tartaric acid, oxalic acid or starch; the amino compound is selected from one of urea, ethylenediamine or ammonia water.
2. The method for preparing pure carbon nanodots according to claim 1, wherein the mass ratio of the inorganic salt, the polyol compound, and the amino compound is 0.5-1.5: 0.5-3: 1.
3. the method for preparing pure carbon nanodots according to claim 1, wherein the product with strong fluorescence is obtained after vacuum heating and then is dialyzed by acidification.
4. A pure carbon nanodot produced by the method according to any one of claims 1 to 3, wherein the pure carbon nanodot is a spherical nanoparticle, and the average particle diameter of the pure carbon nanodot is 2nm to 6 nm.
5. The pure carbon nanodot according to claim 4, wherein the ultraviolet absorption peak of the pure carbon nanodot is at 330nm to 410nm, and the fluorescence emission peak of the aqueous solution of the pure carbon nanodot is at 450nm to 535 nm.
6. An LED light source, which is prepared by the following method: the pure carbon nano-dots according to the claim 4 or 5 and polydimethylsiloxane are mixed according to the mass ratio of 0.1-8:1, then the mixture is coated on an unpackaged LED, and the LED light source is dried, so that the packaged LED light source is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810266517.3A CN108587614B (en) | 2018-03-28 | 2018-03-28 | Pure carbon nanodot, preparation method thereof and LED light source |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810266517.3A CN108587614B (en) | 2018-03-28 | 2018-03-28 | Pure carbon nanodot, preparation method thereof and LED light source |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108587614A CN108587614A (en) | 2018-09-28 |
| CN108587614B true CN108587614B (en) | 2021-09-17 |
Family
ID=63623823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810266517.3A Active CN108587614B (en) | 2018-03-28 | 2018-03-28 | Pure carbon nanodot, preparation method thereof and LED light source |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108587614B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109385274B (en) * | 2018-11-13 | 2021-04-06 | 广东药科大学 | Biomass-based efficient sulfur-nitrogen doped carbon quantum dot and preparation method and application thereof |
| CN110112276A (en) * | 2019-04-30 | 2019-08-09 | 西安交通大学 | It is a kind of can continuous sterilization light emitting device and preparation method thereof |
| CN110669509A (en) * | 2019-09-02 | 2020-01-10 | 上海大学 | Preparation method and application of broad-spectrum polysaccharide carbon quantum dots |
| CN112961669A (en) * | 2021-02-01 | 2021-06-15 | 苏州星烁纳米科技有限公司 | Preparation method of solid-phase carbon quantum dot, solid-phase carbon quantum dot prepared by same and light-emitting device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969348A (en) * | 2016-05-23 | 2016-09-28 | 中国科学院长春光学精密机械与物理研究所 | Carbon nano-point fluorescent powder, preparation method and LED lamp bead |
| CN106833631A (en) * | 2017-02-04 | 2017-06-13 | 中国科学院长春光学精密机械与物理研究所 | A kind of carbon nano dot compound and preparation method thereof, fluorescent material and source material |
-
2018
- 2018-03-28 CN CN201810266517.3A patent/CN108587614B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105969348A (en) * | 2016-05-23 | 2016-09-28 | 中国科学院长春光学精密机械与物理研究所 | Carbon nano-point fluorescent powder, preparation method and LED lamp bead |
| CN106833631A (en) * | 2017-02-04 | 2017-06-13 | 中国科学院长春光学精密机械与物理研究所 | A kind of carbon nano dot compound and preparation method thereof, fluorescent material and source material |
Non-Patent Citations (1)
| Title |
|---|
| Electrostatic Assembly Guided Synthesis of Highly Luminescent Carbon-Nanodots@BaSO4 Hybrid Phosphors with Improved Stability;Ding Zhou et al.;《Small》;20161231;第13卷;第1-10页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108587614A (en) | 2018-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108587614B (en) | Pure carbon nanodot, preparation method thereof and LED light source | |
| Zhang et al. | Synergetic effect of the surfactant and silica coating on the enhanced emission and stability of perovskite quantum dots for anticounterfeiting | |
| Zhang et al. | Fluorescent nanomaterial-derived white light-emitting diodes: what's going on | |
| CN108251117B (en) | Core-shell quantum dot, preparation method thereof and electroluminescent device containing core-shell quantum dot | |
| TW200938609A (en) | Surface-modified phosphors | |
| CN109385273B (en) | Ultra-long-life room temperature phosphorescent material, and preparation method and application thereof | |
| He et al. | Dual‐Protected Metal Halide Perovskite Nanosheets with an Enhanced Set of Stabilities | |
| Chen et al. | Highly efficient and stable luminescence from microbeans integrated with Cd‐free quantum dots for white‐light‐emitting diodes | |
| CN110526277B (en) | Preparation method of doped zinc oxide nanocrystal, electron transport layer and light-emitting device | |
| Zhu et al. | Stable silica coated DDAB-CsPbX3 quantum dots and their application for white light-emitting diodes | |
| CN112442244B (en) | Room-temperature phosphorescent quantum dot material and preparation method and application thereof | |
| CN112521938B (en) | Organic-inorganic hybrid halide luminescent material and preparation method and application thereof | |
| CN106833631B (en) | Carbon nano-dot compound and preparation method thereof, fluorescent powder and light source material | |
| Jang et al. | Near-complete photoluminescence retention and improved stability of InP quantum dots after silica embedding for their application to on-chip-packaged light-emitting diodes | |
| CN113150778A (en) | Aluminum functionalized fluorescent carbon dot and preparation method and application thereof | |
| CN114716996B (en) | Preparation method of mesoporous alumina domain-limited narrow-band green light carbon dot composite fluorescent powder and application of mesoporous alumina domain-limited narrow-band green light carbon dot composite fluorescent powder in liquid crystal backlight source | |
| CN112961669A (en) | Preparation method of solid-phase carbon quantum dot, solid-phase carbon quantum dot prepared by same and light-emitting device | |
| CN110129055B (en) | Preparation of CdSeZnS/ZnS/ZnS core/shell quantum dot | |
| Baek et al. | Mixed halide perovskite nanocrystals with surface engineering based on pseudohalide passivation and Short-Chain ligand exchange for High-Performance blue Light-Emitting diodes | |
| CN110938432A (en) | Preparation method of perovskite quantum dot material | |
| Yang et al. | Magic sol–gel silica films encapsulating hydrophobic and hydrophilic quantum dots for white-light-emission | |
| CN111662715B (en) | Core-shell quantum dot and preparation method thereof, quantum dot film and light-emitting diode | |
| CN110982519A (en) | Carbon nano-dot composite fluorescent powder and preparation method and application thereof | |
| KR20120053312A (en) | Method for preparing cu- and cl-added zns crystalline nano-phosphor materials | |
| Huang et al. | Room temperature synthesis of highly stable near-infrared FAPbI3@ TEOS perovskite phosphor for NIR light-emitting diodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |