CN110330512A - A kind of ag nano-cluster fluorescence nano stick and preparation method thereof and the application in white light LEDs - Google Patents
A kind of ag nano-cluster fluorescence nano stick and preparation method thereof and the application in white light LEDs Download PDFInfo
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- CN110330512A CN110330512A CN201910694647.1A CN201910694647A CN110330512A CN 110330512 A CN110330512 A CN 110330512A CN 201910694647 A CN201910694647 A CN 201910694647A CN 110330512 A CN110330512 A CN 110330512A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000004332 silver Substances 0.000 claims abstract description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 25
- 239000003292 glue Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 13
- 239000003086 colorant Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003446 ligand Substances 0.000 claims description 11
- 239000007848 Bronsted acid Substances 0.000 claims description 10
- 238000002189 fluorescence spectrum Methods 0.000 claims description 10
- 230000005284 excitation Effects 0.000 claims description 9
- 239000002073 nanorod Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000006862 quantum yield reaction Methods 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
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- 230000003760 hair shine Effects 0.000 abstract 1
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- 239000001257 hydrogen Substances 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
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- 229910002699 Ag–S Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- FAKRSMQSSFJEIM-RQJHMYQMSA-N captopril Chemical compound SC[C@@H](C)C(=O)N1CCC[C@H]1C(O)=O FAKRSMQSSFJEIM-RQJHMYQMSA-N 0.000 description 1
- 229960000830 captopril Drugs 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
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- 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
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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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
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
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Abstract
The present invention relates to a kind of ag nano-cluster fluorescence nano sticks and preparation method thereof and the application in white light LEDs, which is by Ag9It is self-assembly of in aqueous solution with hydrochloric acid.Ag prepared by the present invention9Fluorescence nano stick has optical property outstanding, and fluorescence nano stick is lyophilized into the fluorescence property that powder still keeps outstanding, and it can be made into the preferable LED of stabilization of hair orange-red light, it is the LED that the mixing of 10:5:1 ratio can prepare white light emission according to mass ratio simultaneously with commercial blue and green emitting phosphor.The silver cluster that shines can successfully replace the light conversion material of traditional material, provide possibility for the LED of environment-friendly type is made.Silver nanoclusters fluorescence nano stick preparation method of the invention is simple, low in cost；The LED luminous intensity of preparation is excellent, meets the requirement of environmental protection.
Description
Technical field
The present invention relates to a kind of preparation method of ag nano-cluster fluorescence nano stick and its in the application of white light LEDs, belong to
Field of new materials.
Background technique
Light is most important for the study and life of the mankind, and according to statistics, the electric energy that the whole world has more than 20% every year at present is used
In illumination, therefore, how energy conservation and to improve light efficiency particularly critical in lighting area.With traditional fluorescent lamp and incandescent lamp phase
Than the solid-state lighting of, light emitting diode (LED) form have the response time is fast, luminous efficiency is high, can temperature-control range it is wide etc. excellent
Therefore performance is studied more and more widely and is paid close attention to.Up to the present, commercial LED is usually by shining in bluish violet
Color-converting material is coated on InGaN/GaN chip to manufacture.Color-converting material can completely or partially send out chip
It penetrates and is converted to required luminescent color, to generate the LED with visible color or white light.Rare earth phosphor turns material as light
It is alternative, face supply resource is deficient, recovery difficult is big, not environmentally the shortcomings that；And common are machine fluorogen intolerant to photobleaching,
Also limited to applied to LED field；Quantum dot is also considered as competitive color-converting material, but most of about quantum dot
The LED of manufacture, which is depended on, uses the quantum dot (such as cadmium, lead and mercury etc.) containing heavy metal cation, and it is for the body of the mankind
Body health can bring serious influence.Therefore, in order to continue to promote environment-friendly type LED, it is badly in need of finding substitution heavy metal, meets safety
Defined light conversion material.
Recently, metal nanometer cluster can be used as in the led due to its hypotoxicity, low cost and good biocompatibility
Environmental-friendly and biocompatible color-converting material.As novel light-emitting nano material, metal nanometer cluster is usually by several
It is formed to 100 atoms, size is about Fermi's wavelength (< 2nm) of electronics, by realizing metal nanometer cluster periphery ligand
To the electric charge transfer of metal or the interaction of metal-metal, the transmitting of hyperfluorescence may be implemented, outstanding luminescent properties make
Obtaining metal nanometer cluster can be used as LED light transition material.
Ag nano-cluster is widely studied since its excellent performance and raw material easily obtain, about ag nano-cluster
Patent document also has many reports, such as: Chinese patent document CN108372312A (application number: CN201810244736.1)
Disclose a kind of preparation method of hyperfluorescence transmitting ag nano-cluster, it is characterised in that: the Fluorescent silver nanocluster is room temperature
Under using histidine as protective agent and reducing agent, Fluorescent silver nanocluster is prepared by one kettle way as matrix in silver nitrate solution
Solution.Again for example: Chinese patent document CN107225255A (application number: CN201710400091.1) disclose it is a kind of prepare it is glimmering
The method of light silver nanoclusters, which is characterized in that this red fluorescence ag nano-cluster is using captopril as protective agent, boron hydrogen
Change sodium as reducing agent, in alkaline environment, is prepared by " one kettle way ".Chinese patent document CN109111912A is public
A kind of high power white LED nano-cluster core-shell fluorescent powder and preparation method thereof has been opened, nano silver cluster is prepared by hydro-thermal method and is repaired
The nucleocapsid fluorescence transition material of decorations, the doping of Bi/Mn double ion can be with by adjusting doping coefficient, doping ratio, ionic valence condition etc.
Regulation fluorescent powder realizes ultraviolet and blue light region biabsorption, while generating the high-intensitive transmitting of blue and green light, yellow light, red light district.
However, above-mentioned material is primarily present following deficiency: 1. contain Determination of multiple metal elements, and are fluorides, result in waste of resources and
Environmental disruption；2. preparation method is cumbersome, hydro-thermal method has been used, has increased production cost.
Currently, the exploration of synthetic method and the research of solid state properties are only limited to for silver nanoclusters report, for regulation
Ag nano-cluster aggregation pattern in aqueous solution and its rarely has report in the application study of LED field as light conversion material
Road.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provide a kind of ag nano-cluster fluorescence nano stick and preparation method thereof with
The application of white light LEDs.
Term explanation:
Ag9: it is a kind of ag nano-cluster of nine cores, due to the π-π effect between ligand, ligand is made to the electric charge transfer of metal
It is acted on, ligand to metal-metal electric charge transfer and the interaction of metal-metal, Ag9With certain luminosity.
Technical scheme is as follows:
A kind of ag nano-cluster fluorescence nano stick, the nanometer rods are with Bronsted acid to Ag9Solution proton obtains；
The Bronsted acid is HCl or HBr；The Ag9It is using Ag as core, using 4- mercaptobenzoic acid as nine cores of ligand
Ag nano-cluster.
, according to the invention it is preferred to, ag nano-cluster fluorescence nano stick the diameter 20-30nm, length 300-
400nm。
, according to the invention it is preferred to, the fluorescence spectrum of the ag nano-cluster fluorescence nano stick shows that excitation wavelength is
300- 520nm, launch wavelength 550-800nm.
, according to the invention it is preferred to, the quantum yield of the ag nano-cluster fluorescence nano stick is 5-6%.
According to the present invention, the preparation method of above-mentioned ag nano-cluster fluorescence nano stick, comprises the following steps that
By silver nitrate (AgNO3) and 4- mercaptobenzoic acid (H2Mba it) is dispersed in water and is ultrasonically treated, at ultrasound
Ammonium hydroxide (NH is added during reason into said mixture3·H2O), the Ag of yellow transparent is obtained9Solution；By Ag9Aqueous solution and matter
Sub- acid-mixed is closed, and is vortexed, and is stood to get ag nano-cluster fluorescence nano stick aqueous solution.
, according to the invention it is preferred to, AgNO3The concentration for being distributed to the aqueous solution in water is 1mmolL-1,H2Mba dispersion
The concentration 1mmolL of aqueous solution into water-1；AgNO3And H2The molar ratio of mba is 1:1；
Preferably, the supersonic frequency of ultrasonic treatment is 30~50kHz, and ultrasonic power 80W, ultrasonic time is 20~30 points
Clock.
, according to the invention it is preferred to, the mass concentration of ammonium hydroxide is 25%；The additional amount of ammonium hydroxide is that will precipitate dissolution to be entirely
Only.Obtained solution is yellow clear solution.
, according to the invention it is preferred to, Ag9Aqueous solution is with the mixed proportion of Bronsted acid according to protonic acid aqueous solution after mixing
Molar concentration is 28~32mmolL-1, Ag9The molar concentration of aqueous solution is 7-9mmolL-1Meter.Preferably, protonic acid solution
It is 12molL that molar concentration, which can be used,-1Concentrated acid configuration.The Bronsted acid is HCl or HBr.
, according to the invention it is preferred to, vortex time is 20~30s, and time of repose is 1-7 days.
According to the present invention, above-mentioned ag nano-cluster fluorescence nano stick aqueous solution is lyophilized, powder can be obtained.
According to the present invention, above-mentioned ag nano-cluster fluorescence nano stick is preparing the application in white light LEDs.By above-mentioned silver nanoparticle
Cluster fluorescence nano stick is mixed with the fluorescent powder of different colours, and the LED of different colours can be obtained.
, according to the invention it is preferred to, the white light LEDs are prepared as follows to obtain:
Ag nano-cluster fluorescence nano stick aqueous solution is lyophilized into powder, grinding uniformly, then with different colours fluorescent powder
It is uniformly mixed, is then deposited in LED chip by glue, solidifies the LED to get different colours.
, according to the invention it is preferred to, freeze temperature is -60 DEG C, and freeze-drying time is 24 hours.Gained fluorescence nano stick it is glimmering
The quantum yield of light powder is 5-6%.
, according to the invention it is preferred to, the fluorescent powder of the different colours can be orange red, blue or/and green, quality point
It Wei not 10mg, 5mg and 2mg.
, according to the invention it is preferred to, glue deposition glue used is high refractive power LED patch silica gel A glue and B glue, mixes matter
Amount is than being 1:4.
, according to the invention it is preferred to, the excitation wavelength of the LED chip is 365nm, light efficiency 0.9lm/W；
Preferably, the drying temperature of curing process is 60 DEG C, and curing time is 3 hours.
The principle of the present invention:
Ag prepared by the present invention9Aqueous solution is that fluorescence by the addition of the Bronsted acids such as hydrochloric acid does not make Ag at room temperature9
The carboxylate radical protonation of the ligand of periphery, by hydrogen bond action, π-π effect limits the rotation and vibration of ligand well, realizes
Ligand makes ag nano-cluster nanometer rods show significant photoluminescent property to the electronics transfer effect between metal.By hyperfluorescence
Ag9Nanometer rods aqueous solution is lyophilized into powder and mixes according to a certain percentage with commercial fluorescent powder, and white light can be made i.e. not
With the LED light of color.
Outstanding feature and beneficial effect of the invention is:
1, Ag in the present invention9It is the noble metal cluster compound that size is less than 2nm, belongs to new inorganic material, structure novel, property
Matter is unique；Using the method for Supramolecular self assembly, the nanometer rods of ordered structure have been constructed, thus realize the transmitting of fluorescence, meanwhile,
Fluorescence nano stick remains the photoluminescent property under solid state.
2, the Ag of fluorescent emission prepared by the present invention9Aqueous solution, aggregation pattern can realize shape by the concentration of adjusting hydrochloric acid
The regulation of looks.
3, glo-stick of the invention has strong fluorescent characteristic, in Ag9Component is used as the color in 365nm LED chip and turns
Layer is changed, white light LEDs (WLED) prototype is demonstrated.Fluorescence radiation can be realized in glo-stick of the invention in aqueous solution, fills up
Existing fluorescent material can not fluorescence radiation in aqueous solution blank.
4, ag nano-cluster fluorescence nano stick of the invention can successfully replace the light conversion material of traditional material, can make
Obtain the LED of environment-friendly type.
5, silver nanoclusters fluorescence nano stick preparation method of the invention is simple, low in cost；The LED luminous intensity of preparation is excellent
It is different, meet the requirement of environmental protection.
Material characteristics set forth in the present invention are tested using the following method:
1, transmission electron microscope (TEM).The pattern of fluorescence nano stick can be observed by TEM.
2, fluorescence spectrum.The fluorescence intensity of fluorescence nano stick is tested by sepectrophotofluorometer.
3, X-ray diffraction (XRD).Nanometer rods active force can be characterized by XRD.
4, fourier transform infrared spectroscopy (FT-IR).The Ag of protonation can be characterized by FT-IR spectrogram9Interaction.
Detailed description of the invention
Fig. 1 is substance A g synthesized by the embodiment of the present invention 19Molecular structure model figure.
Fig. 2 is the TEM figure that the present invention prepares ag nano-cluster glo-stick.Wherein: (a) being embodiment 1, (b) be embodiment
2, (c) it is embodiment 3, (d) is embodiment 4.
Fig. 3 is the infrared waves spectrogram that the embodiment of the present invention 2 prepares ag nano-cluster fluorescence nano stick, in which: (a) is fluorescence
Nanometer rods (b) are Ag9。
Fig. 4 is the XRD diagram that the embodiment of the present invention 2 prepares ag nano-cluster fluorescence nano stick, in which: (a) receives for fluorescence
Rice stick (b) is Ag9。
Fig. 5 is the fluorescence spectra of ag nano-cluster fluorescence nano stick prepared by the embodiment of the present invention 1.
The ultraviolet light irradiation that the sample of hair different colours light is 365nm in wavelength obtained by Fig. 6 is 5-7 of the embodiment of the present invention
Under optical photograph.Wherein: (a) being embodiment 5, (b) be embodiment 6, (c) be embodiment 7.
Fig. 7 be the made preparation different colours light of 5-8 of the embodiment of the present invention LED 365nm excitation under optical picture.Wherein:
(a) it is embodiment 5, (b) is embodiment 6, (c) be embodiment 7, (d) is embodiment 8.
Fig. 8 is the fluorescence spectrum of the LED of the made preparation different colours light of 5-8 of the embodiment of the present invention.Wherein: being (a) implementation
Example 5 (b) is embodiment 6, (c) is embodiment 7, (d) is embodiment 8.
Fig. 9 is the CIE color chart of the made preparation different colours light of 5-8 of the embodiment of the present invention.Wherein: orange red is embodiment
5, blue is embodiment 6, and green is embodiment 7, and white is embodiment 8.
Figure 10 is the TEM figure of ag nano-cluster different-shape prepared by comparative example 1-2 of the present invention.Wherein: (a) being comparative example
1, it (b) is comparative example 2.
Specific embodiment
The present invention is further elaborated with attached drawing combined with specific embodiments below, but not limited to this.
Raw materials used in embodiment is conventional raw material, commercial products, in which: AgNO3It buys close europeanized in Tianjin section
Learn reagent Co., Ltd, H2Mba purchase is in Sigma-Aldrich, and concentrated hydrochloric acid, the purchase of green and blue fluorescent powder are in Jinan City
Sai Bo chemical reagent Co., Ltd.
Embodiment 1
A kind of preparation method of ag nano-cluster fluorescence nano stick, comprises the following steps that
(1)Ag9The synthesis of molecule
Accurately weigh AgNO3(1mmol, 170mg) and H2Mba (1mmol, 155mg) be dispersed in 6mL water and
It is ultrasonically treated in KQ5200DE instrument at 20 minutes (80W, 40kHz), in ultrasonication into said mixture
NH is added3·H2O (25%, 0.5mL), obtains the Ag of yellow transparent9Solution.
(2) preparation of aqueous hydrochloric acid solution
Concentrated hydrochloric acid liquid is accurately pipetted, water three times is added, meter measurement is tried with pH, prepares the aqueous hydrochloric acid solution of pH=1；
(3) preparation of silver nanoclusters glo-stick
Measure the Ag of 50 μ L9Aqueous solution is added 670 μ L water three times, adds the hydrochloric acid of 280 μ L pH=1, and be vortexed 30 s
Make its be uniformly mixed, after mixing concentration of hydrochloric acid be 28mmol/L, stood in 20 DEG C of insulating boxs for 24 hours to get.
The Ag that the present embodiment obtains9Molecular structure it is as shown in Figure 1.Ag as shown in Figure 19It is using Ag as core, with 4- sulfydryl
Benzoic acid is the ag nano-cluster of nine cores of ligand.
The present embodiment obtains the TEM figure of ag nano-cluster fluorescence nano stick, as shown in Fig. 2 (a).By Fig. 2 (a) it is found that silver
The structure of nanocluster fluorescence nano stick presentation ordering rule.Nanorod diameter 20-30nm, length 300-400nm.
The present embodiment prepares the infrared waves spectrogram of ag nano-cluster fluorescence nano stick as shown in figure 3, wherein: (a) being fluorescence
Nanometer rods (b) are Ag9.From the figure 3, it may be seen that the formation of nanometer rods is mainly driven by hydrogen bond action.
The XRD diagram of ag nano-cluster fluorescence nano stick manufactured in the present embodiment is as shown in Figure 4, in which: (a) receives for fluorescence
Rice stick (b) is Ag9.As shown in Figure 4, there are orderly structures for nanometer rods, and the presence for having Ag-Ag, Ag-S and π-π to act on.
The fluorescence spectra of ag nano-cluster fluorescence nano stick manufactured in the present embodiment is as shown in figure 5, as shown in Figure 5, have
More wide excites scope, best excitation is 500nm, and best transmitting is 615nm, and have biggish Stokes displacement (~
100nm)。
Embodiment 2
As described in Example 1, a kind of preparation method of ag nano-cluster fluorescence nano stick, comprises the following steps that
Measure the Ag of 50 μ L9Aqueous solution is added 650 μ L water three times, adds the hydrochloric acid of 300 μ L pH=1, and be vortexed 30 s
Make its be uniformly mixed, after mixing concentration of hydrochloric acid be 30mmol/L, stood in 20 DEG C of insulating boxs for 24 hours to get.
The Ag that the present embodiment obtains9Molecular structure it is as shown in Figure 1.Ag as shown in Figure 19It is a kind of silver nanoparticle of nine cores
Cluster.
The present embodiment obtains the TEM figure of ag nano-cluster fluorescence nano stick, as shown in Fig. 2 (b).Ag nano-cluster fluorescence is received
The structure of ordering rule is presented in rice stick.Nanorod diameter 20-30nm, length 300-400nm.
Embodiment 3
As described in Example 1, a kind of preparation method of ag nano-cluster fluorescence nano stick, comprises the following steps that
Measure the Ag of 50 μ L9Aqueous solution is added 630 μ L water three times, adds the hydrochloric acid of 320 μ L pH=1, and be vortexed 30 s
Make its be uniformly mixed, after mixing concentration of hydrochloric acid be 32mmol/L, stood in 20 DEG C of insulating boxs for 24 hours to get.
The Ag that the present embodiment obtains9Molecular structure it is as shown in Figure 1.Ag as shown in Figure 19It is a kind of silver nanoparticle of nine cores
Cluster.
The present embodiment obtains the TEM figure of ag nano-cluster fluorescence nano stick, as shown in Fig. 2 (c).Ag nano-cluster fluorescence is received
The structure of ordering rule is presented in rice stick.Nanorod diameter 20-30nm, length 300-400nm.
Embodiment 4
As described in Example 1, a kind of preparation method of ag nano-cluster fluorescence nano stick, comprises the following steps that
Measure the Ag of 50 μ L9Aqueous solution is added 630 μ L water three times, adds the HBr of 300 μ L pH=1, and 30 s that are vortexed make
It is uniformly mixed, after mixing HBr concentration be 30mmol/L, stood in 20 DEG C of insulating boxs for 24 hours to get.
The Ag that the present embodiment obtains9Molecular structure it is as shown in Figure 1.Ag as shown in Figure 19It is a kind of silver nanoparticle of nine cores
Cluster.
The present embodiment obtains the TEM figure of ag nano-cluster fluorescence nano stick, as shown in Fig. 2 (d).Ag nano-cluster fluorescence is received
The structure of ordering rule is presented in rice stick.Nanorod diameter 20-30nm, length 300-400nm.
Embodiment 5
A kind of preparation method for the LED sending out orange-red light, comprises the following steps that
Fluorescence nano stick is lyophilized into powder, nanometer rods powder 5mg is accurately weighed, is fully ground with mortar, is then distinguished
The quality for accurately weighing high refractive power LED patch silica gel A glue and B glue is 5mg and 20mg, carried out according to mass ratio 1:4 it is uniformly mixed,
And be uniformly mixed sample powder with business glue, the mixing mucus of about beans size is taken, it is deposited on commercially available LED core
On piece, and solidify in 60 DEG C of baking oven 3 hours to manufacture LED.
The present embodiment obtains the LED figure of hair orange-red light as shown in Fig. 7 (a).Spectrum analysis shows the present embodiment preparation orange
Red light LED chromaticity coordinates of gained fluorescence emission spectrum in the case where excitation wavelength is 365nm is (0.59,0.41).
Embodiment 6
A kind of preparation method of the LED for the coloured light that turns blue, comprises the following steps that
Commercial blue fluorescent powder 5mg is accurately weighed, is fully ground with mortar, then accurately weighs high refractive power LED patch respectively
Piece silica gel A glue and B colloid amount are 5mg and 20mg, carried out according to mass ratio 1:4 it is uniformly mixed, and by sample powder and business glue
Mixing, takes the mixing mucus of about beans size, it is deposited in commercially available LED chip, and solidify 3 in 60 DEG C of baking oven
Hour manufactures LED.
The present embodiment obtain turning blue coloured light LED figure as shown in Fig. 7 (b).Spectrum analysis shows the present embodiment preparation blue
Light LED chromaticity coordinates of gained fluorescence emission spectrum in the case where excitation wavelength is 365nm is (0.14,0.06).
Embodiment 7
A kind of preparation method of the LED of glow green, comprises the following steps that
Commercial green emitting phosphor 5mg is accurately weighed, is fully ground with mortar, then accurately weighs high refractive power LED patch respectively
Piece silica gel A glue and B colloid amount are 5mg and 20mg, carried out according to mass ratio 1:4 it is uniformly mixed, and by sample powder and business glue
Mixing, takes the mixing mucus of about beans size, it is deposited in commercially available LED chip, and solidify 3 in 60 DEG C of baking oven
Hour manufactures LED.
The present embodiment obtains the LED figure of glow green as shown in Fig. 7 (c).Spectrum analysis shows that the present embodiment prepares green light
LED chromaticity coordinates of gained fluorescence emission spectrum in the case where excitation wavelength is 365nm is (0.03,0.64).
Embodiment 8
A kind of preparation method of the LED to emit white light, comprises the following steps that
Accurately weigh respectively fluorescence nano stick, blue colour fluorescent powder, green emitting phosphor quality be 20mg, 10mg and 2mg.It is logical
Cross the charge ratio group for being 10:5:1 according to mass ratio by three kinds of fluorescent powders (fluorescence nano stick, blue colour fluorescent powder, green emitting phosphor)
It closes, is fully ground three kinds of fluorescent powders with mortar, be uniformly mixed, then accurately weigh mixed powder 5mg.High refractive power is accurately weighed again
LED patch silica gel A glue and B colloid amount are 5mg, 20mg, carried out according to mass ratio 1:4 it is uniformly mixed, and by sample powder and quotient
Industry glue is uniformly mixed, and takes the mixing mucus of about beans size, they are deposited in commercially available LED chip, and at 60 DEG C
Solidify 3 hours in baking oven to manufacture LED.
The LED figure that the present embodiment is emitted white light is as shown in Fig. 7 (d).Spectrum analysis shows that the present embodiment prepares white light
LED chromaticity coordinates of gained fluorescence emission spectrum in the case where excitation wavelength is 365nm is (0.33,0.32).
Comparative example 1
As described in Example 1, the Ag of 50 μ L is measured9Aqueous solution is added 700 μ L water three times, adds 250 μ L pH=1's
Hydrochloric acid, vortex 30s are uniformly mixed it, and concentration of hydrochloric acid is 25mmol/L after mixing, stand for 24 hours in 20 DEG C of insulating boxs, i.e.,
?.
This comparative example obtains the TEM figure of product, as shown in Figure 10 (a).By Figure 10 (a) it is found that product is ag nano-cluster
The structure of ordering rule, nanometer bulb diameter 10-20nm is presented in nanosphere.As it can be seen that causing since the concentration of hydrochloric acid after mixing is too low
It cannot get Silver nanorod, but nanosphere.
Comparative example 2
As described in Example 1, the Ag of 50 μ L is measured9Aqueous solution is added 650 μ L water three times, adds 300 μ L pH=1's
HI, vortex 30s make its be uniformly mixed, after mixing HI concentration be 30mmol/L, stood in 20 DEG C of insulating boxs for 24 hours to get.
This comparative example obtains the TEM figure of product, as shown in Figure 10 (b).By Figure 10 (b) it is found that product is ag nano-cluster
The structure of ordering rule, nanometer bulb diameter 30-60nm is presented in nanosphere.Ag nano-cluster nanosphere does not have fluorescence radiation spy
Property.As it can be seen that lead to cannot get Silver nanorod using HI, but nanosphere.Illustrate and not all Bronsted acid can be obtained successfully
Silver nanorod.
Comparative example 3
The transmitting of fluorescence all may be implemented by modification (means such as ligand modified, self assembly) in ag nano-cluster at present.In
State patent document CN104588645A (application number: CN201510059292.0) discloses a kind of Yin Na of the galactic nucleus of different number
Rice cluster aqueous solution, aqueous solution do not have luminescent properties, are applied to antibacterial experiment；Chinese patent document CN108817417A
(application number: CN201810867437.3) discloses a kind of non-luminous near-spherical nano silver slice cluster, and solid powder does not have
Preparation optical property.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, based on the technical solutions of the present invention, those skilled in the art are not needed to make the creative labor and can be done
Various modifications or changes out are still within protection scope of the present invention.
Claims (10)
1. a kind of ag nano-cluster fluorescence nano stick, which is characterized in that the nanometer rods are with Bronsted acid to Ag9Solution proton
It obtains；
The Bronsted acid is HCl or HBr；The Ag9It is using Ag as core, using 4- mercaptobenzoic acid as the silver of nine cores of ligand
Nanocluster.
2. ag nano-cluster fluorescence nano stick according to claim 1, which is characterized in that the ag nano-cluster fluorescence
Nanorod diameter 20-30nm, length 300-400nm.
3. ag nano-cluster fluorescence nano stick according to claim 1, which is characterized in that the ag nano-cluster fluorescence
The fluorescence spectrum of nanometer rods shows, excitation wavelength 300-520nm, launch wavelength 550-800nm；
Preferably, the quantum yield of the ag nano-cluster fluorescence nano stick is 5-6%.
4. the preparation method of ag nano-cluster fluorescence nano stick described in claim 1, comprises the following steps that
By silver nitrate (AgNO3) and 4- mercaptobenzoic acid (H2Mba it) is dispersed in water and is ultrasonically treated, had been ultrasonically treated
Ammonium hydroxide (NH is added in Cheng Zhongxiang said mixture3·H2O), the Ag of yellow transparent is obtained9Solution；By Ag9Aqueous solution and Bronsted acid
Mixing, is vortexed, and stands to get ag nano-cluster fluorescence nano stick aqueous solution.
5. the preparation method of ag nano-cluster fluorescence nano stick according to claim 4, which is characterized in that AgNO3It is distributed to
The concentration of aqueous solution in water is 1mmolL-1,H2Mba is distributed to the concentration 1mmolL of the aqueous solution in water-1；AgNO3With
H2The molar ratio of mba is 1:1；
Preferably, the supersonic frequency of ultrasonic treatment is 30~50kHz, and ultrasonic power 80W, ultrasonic time is 20~30 minutes；
Preferably, the mass concentration of ammonium hydroxide is 25%；The additional amount of ammonium hydroxide is until precipitating dissolution completely.
6. the preparation method of ag nano-cluster fluorescence nano stick according to claim 4, which is characterized in that Ag9Aqueous solution with
The mixed proportion of Bronsted acid is 28~32mmolL according to the molar concentration of protonic acid aqueous solution after mixing-1, Ag9Aqueous solution
Molar concentration is 7-9mmolL-1Meter.
7. the preparation method of ag nano-cluster fluorescence nano stick according to claim 4, which is characterized in that vortex time is
20~30s, time of repose are 1-7 days.
8. ag nano-cluster fluorescence nano stick described in claim 1 is preparing the application in white light LEDs.
9. application according to claim 8, which is characterized in that the white light LEDs are prepared as follows to obtain:
Ag nano-cluster fluorescence nano stick aqueous solution is lyophilized into powder, grinding uniformly, is then mixed with different colours fluorescent powder
Uniformly, it is then deposited in LED chip by glue, solidifies the LED to get different colours.
10. application according to claim 9, which is characterized in that freeze temperature is -60 DEG C, and freeze-drying time is 24 hours；
Preferably, the fluorescent powder of the different colours can be orange red, blue or/and green, quality be respectively 10mg, 5mg and
2mg；
Preferably, glue deposition glue used is high refractive power LED patch silica gel A glue and B glue, mixing mass ratio 1:4.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111739997A (en) * | 2020-07-03 | 2020-10-02 | 青岛科技大学 | White light LED (light emitting diode) capable of emitting light by exciting gold-silver alloy clusters through blue light and preparation method thereof |
| CN111739998A (en) * | 2020-07-03 | 2020-10-02 | 青岛科技大学 | High-color-rendering white light LED based on silver clusters and preparation method thereof |
| CN114032089A (en) * | 2021-11-25 | 2022-02-11 | 山东大学 | Silver nanocluster fluorescent nanotube, preparation method thereof and application thereof in arginine detection |
| CN114525125A (en) * | 2022-02-15 | 2022-05-24 | 山东大学 | Water-soluble 'atom accurate' Ag6Nanocluster and macro synthesis method and application thereof |
| CN116254105A (en) * | 2023-02-27 | 2023-06-13 | 山东大学 | Near infrared emission silver nanocluster/polymer composite material with photo-thermal conversion performance and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015007293A1 (en) * | 2013-07-19 | 2015-01-22 | University Of Copenhagen | Stem-loop silver nanocluster probes for mirna detection |
| CN104588645A (en) * | 2015-02-04 | 2015-05-06 | 山西大学 | Silver nanometer cluster compound with antibacterial activity and preparation method thereof |
| CN107225255A (en) * | 2017-05-31 | 2017-10-03 | 山西大学 | A kind of red fluorescence ag nano-cluster probe and its preparation method and application |
| CN107254307A (en) * | 2017-06-13 | 2017-10-17 | 山东大学 | A kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection Fe3+Application |
| CN108372312A (en) * | 2018-03-23 | 2018-08-07 | 山西大学 | A kind of green fluorescence ag nano-cluster and the preparation method and application thereof |
| CN108817417A (en) * | 2018-09-04 | 2018-11-16 | 电子科技大学中山学院 | Preparation method of sphere-like nano silver sheet cluster |
| CN109111912A (en) * | 2018-10-17 | 2019-01-01 | 广东远合工程科技有限公司 | A kind of preparation of high power white LED nano-cluster core-shell fluorescent powder |
-
2019
- 2019-07-30 CN CN201910694647.1A patent/CN110330512B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015007293A1 (en) * | 2013-07-19 | 2015-01-22 | University Of Copenhagen | Stem-loop silver nanocluster probes for mirna detection |
| CN104588645A (en) * | 2015-02-04 | 2015-05-06 | 山西大学 | Silver nanometer cluster compound with antibacterial activity and preparation method thereof |
| CN107225255A (en) * | 2017-05-31 | 2017-10-03 | 山西大学 | A kind of red fluorescence ag nano-cluster probe and its preparation method and application |
| CN107254307A (en) * | 2017-06-13 | 2017-10-17 | 山东大学 | A kind of silver nanoclusters fluorescence vesica and preparation method thereof and detection Fe3+Application |
| CN108372312A (en) * | 2018-03-23 | 2018-08-07 | 山西大学 | A kind of green fluorescence ag nano-cluster and the preparation method and application thereof |
| CN108817417A (en) * | 2018-09-04 | 2018-11-16 | 电子科技大学中山学院 | Preparation method of sphere-like nano silver sheet cluster |
| CN109111912A (en) * | 2018-10-17 | 2019-01-01 | 广东远合工程科技有限公司 | A kind of preparation of high power white LED nano-cluster core-shell fluorescent powder |
Non-Patent Citations (2)
| Title |
|---|
| SAIFEI PAN ET AL.: "Hydrophobicity-guided self-assembled particles of silver nanoclusters with aggregation-induced emission and their use in sensing and bioimaging", 《JOURNAL OF MATERIALS CHEMISTRY B》 * |
| WENJUN DU ET AL.: "Ag50(Dppm)6(SR)30 and Its Homologue AuxAg50-x(Dppm)6(SR)30 Alloy Nanocluster: Seeded Growth, Structure Determination, and Differences in Properties", 《JOURNAL OF THE AMERICANC CHEMISTRY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111739997A (en) * | 2020-07-03 | 2020-10-02 | 青岛科技大学 | White light LED (light emitting diode) capable of emitting light by exciting gold-silver alloy clusters through blue light and preparation method thereof |
| CN111739998A (en) * | 2020-07-03 | 2020-10-02 | 青岛科技大学 | High-color-rendering white light LED based on silver clusters and preparation method thereof |
| CN114032089A (en) * | 2021-11-25 | 2022-02-11 | 山东大学 | Silver nanocluster fluorescent nanotube, preparation method thereof and application thereof in arginine detection |
| CN114032089B (en) * | 2021-11-25 | 2022-06-28 | 山东大学 | Silver nanocluster fluorescent nanotube, preparation method thereof and application thereof in arginine detection |
| US11891553B2 (en) * | 2021-11-25 | 2024-02-06 | Shandong University | Silver nanocluster fluorescent nanotube, a preparation method and its application in the detection of arginine |
| CN114525125A (en) * | 2022-02-15 | 2022-05-24 | 山东大学 | Water-soluble 'atom accurate' Ag6Nanocluster and macro synthesis method and application thereof |
| CN116254105A (en) * | 2023-02-27 | 2023-06-13 | 山东大学 | Near infrared emission silver nanocluster/polymer composite material with photo-thermal conversion performance and preparation method thereof |
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