CN107338042A - Full color emission copper cluster assembly fluorescent material, preparation method and its application in white light LED part of solvent regulation and control - Google Patents
Full color emission copper cluster assembly fluorescent material, preparation method and its application in white light LED part of solvent regulation and control Download PDFInfo
- Publication number
- CN107338042A CN107338042A CN201710579460.8A CN201710579460A CN107338042A CN 107338042 A CN107338042 A CN 107338042A CN 201710579460 A CN201710579460 A CN 201710579460A CN 107338042 A CN107338042 A CN 107338042A
- Authority
- CN
- China
- Prior art keywords
- fluorescent material
- copper
- full color
- solvent
- color emission
- 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.)
- Granted
Links
- 239000010949 copper Substances 0.000 title claims abstract description 102
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 98
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000033228 biological regulation Effects 0.000 title claims abstract description 15
- 239000002904 solvent Substances 0.000 title claims description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000005253 cladding Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000005286 illumination Methods 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 claims description 27
- -1 alkyl hydrosulfide Chemical compound 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000002604 ultrasonography Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 238000005119 centrifugation Methods 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical group CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- FTBCOQFMQSTCQQ-UHFFFAOYSA-N 4-bromobenzenethiol Chemical class SC1=CC=C(Br)C=C1 FTBCOQFMQSTCQQ-UHFFFAOYSA-N 0.000 claims description 2
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical group SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 238000012546 transfer Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 description 14
- 241000446313 Lamella Species 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 9
- 230000007547 defect Effects 0.000 description 7
- 230000005284 excitation Effects 0.000 description 7
- 238000002189 fluorescence spectrum Methods 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 241000894007 species Species 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000003948 formamides Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
-
- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Luminescent Compositions (AREA)
Abstract
It is a kind of to regulate and control photochromic high brightness full color emission copper cluster assembly fluorescent material, preparation method and its application in fine copper cluster White-light LED illumination device is prepared that whole visible region is covered in 490~670nm using different types of reaction dissolvent, belong to full color emission metal cluster assembly preparing technical field.The present invention uses colloidal solution one kettle way, aromatic series and aliphatic sulfydryl cladding part, by changing reaction dissolvent species, under stirring at room temperature, the two-dimentional assembly fluorescent material for the full color emission assembled by copper cluster that can be stablized, its is photochromic in 490~670nm continuously adjustabes.The assembly method of manufacturing fluorescent material is simple, fast, safety non-pollution, it can be mass, it is especially easy, photochromic to photochromic regulation to cover whole visible region, and obtained material while there is high brightness and good stability, and when premixing white light, unstressed configuration is quenched or energy transfer phenomenon occurs, therefore the assembly fluorescent material can apply to high performance White-light LED illumination field.
Description
Technical field
The invention belongs to full color emission metal cluster assembly preparing technical field, and in particular to one kind utilizes different types of
Photochromic full color emission copper cluster assembly fluorescent material, the preparation that whole visible region is covered in 490~670nm of reaction dissolvent regulation and control
Method and its application in fine copper cluster White-light LED illumination device is prepared.
Background technology
Fluorescence metal nano-cluster received wide in recent years as the fluorescent material for having potential illumination and display application
General concern.Although the research of gold and silver fluorescence nano cluster is increasingly ripe, it is more suitable for the fluorescence copper cluster of commercial applications because of it
Stability is poor, and brightness is low and photochromic controllability is poor, limits its research and application in White-light LED illumination field.Carry
The bright means of high metal cluster rigidifying part shell method, increase part electron rich it has been reported that such as aggregation-induced emission method
Group methodologies etc.；But be still only limitted to change ligand species in photochromic regulation or change metal core size, method is single, multiple
Miscellaneous, poor controllability.From the aspect of practical, new simple synthesis is opened up, is highlighted, stable especially photochromic company
Continuous adjustable cheap nanocluster fluorescence material turns into the focus that each side is explored.
Secondly the white light parts that luminescent layer constructs are done by simple metal cluster, fluorescence metal single cluster majority has aggregation inducing and is quenched
Effect, obtained fluorescent powder are luminous extremely faint；Or there is energy transfer situation in different photochromic raw material premix, to system
Difficulty is brought as technique.
Based on above reason, a kind of method of new facile syntheesis metal cluster assembly Full color is we provided, profit
It is different with the embedded defect or cosmetic bug that different types of reaction dissolvent is different to the coordination ability of copper and then is formed, synthesize
The fluorescence copper cluster of photochromic covering blue light to the whole visible region of feux rouges (490~670nm) assembles induced luminescence material.Assembling also increases
Strong brightness and stability, and assembly materials do not have fluorescent quenching and energy transfer phenomenon when premix constructs white light,
Based on this, it is blended using obtained blue and green light and feux rouges copper cluster assembly materials, has constructed and be based on fine copper cluster assembly materials
White light parts.This research has very big to the development based on copper cluster Full color field and metal cluster white-light illuminating field
Meaning.
The content of the invention
It is an object of the invention to provide a kind of the full color emission copper cluster assembly fluorescent material and its system of new solvent regulation and control
Preparation Method, the photochromic copper cluster assembly fluorescence in visible region continuously adjustabe is prepared using the reaction dissolvent of differing dielectric constant
Material and its application in fine copper cluster White-light LED illumination device is prepared.
Difference of the synthetic method using variety classes reaction dissolvent to cupric coordination ability, in the synthetically prepared process of assembly
In be pre-dissolved copper source solvent and can introduce embedded defect, main body reaction dissolvent can introduce cosmetic bug, with the change of solvent dielectric constant
Change, quantity is different the defects of introducing, and these defects also can while the stability of fluorescence nano cluster, fluorescence quantum yield is influenceed
Influence glow color.So subsequent assembly and regulation process, it is only necessary to according to target capabilities such as the glow colors finally needed, change
Become the experiment parameter such as reaction dissolvent species or proportioning, method is simple, safety.
The assembly fluorescent material utilizes the assembling induced luminescence characteristic of metal cluster, to its pattern while improving brightness
And glow color is regulated and controled.Because the assembly fluorescent material Modulatory character is strong, photochromic wide coverage, preparation method letter
It is single, quick, it can be mass, low raw-material cost, technique nontoxic pollution-free, and obtained material brightness and stability all obtain
To raising, full color emission is realized in visible region, and when premixing white light, noenergy shifts, therefore the assembly fluorescent material
It can apply to White-light LED illumination field.
The present invention uses colloidal solution one kettle way, and using higher boiling main body reaction dissolvent, a small amount of low boiling copper source is pre-dissolved molten
Agent, alkyl hydrosulfide or aromatic thiol cladding part, pass through simple stirring at normal temperature, you can that is stablized is assembled by copper cluster
Transverse and longitudinal is can reach by simply changing reaction dissolvent species this synthesis condition than different lamella assembly fluorescent materials
Regulation and control to fluorescent emission peak position.
Specifically, the preparation method of copper cluster assembly fluorescent material of the present invention, its step are as follows：
Copper source is fully immersed into low boiling in advance to be pre-dissolved in the solvent of copper source, 2~5min of ultrasound, then dissolved in above-mentioned solution
In higher boiling main body reaction dissolvent, it is 1 that low boiling, which is pre-dissolved copper source solvent and the volumetric usage ratio of higher boiling main body reaction dissolvent,：10
~50, copper source is 10~50% in the mass concentration that low boiling is pre-dissolved in the solvent of copper source；Room temperature adds alkyl sulfide under magnetic agitation
The mole dosage ratio in alcohol or aromatic thiol cladding part, part and copper source is 5~30：1,2~5min of ultrasound is allowed to well mixed,
Then 2min~1h is stirred at room temperature, and dichloromethane and ethanol are added into obtained white suspension, after shaking up, 2000~
5000r/min centrifuges 2~5min, and the volumetric usage ratio of white suspension, dichloromethane and ethanol is 1：1~3：2~6；Again will
Obtained centrifugation product vacuum obtains alkyl hydrosulfide after draining or aromatic thiol coats being assembled by copper cluster for part stabilization
Size transverse and longitudinal than different lamella assembly fluorescent materials；By the species, the kind of high boiling solvent that change low boiling point solvent
Class and low boiling are pre-dissolved the ratio of solvent and higher boiling bulk solvent, you can it is continuous to the different transmitting peak positions of feux rouges to obtain blue light
Adjustable fine copper cluster assembly Full color material.
White light LED part is prepared based on copper cluster assembly luminescent material：By blue light copper cluster assembly fluorescent material, green glow copper
Cluster assembly fluorescent material and feux rouges copper cluster assembly fluorescent material are well mixed with polydimethylsiloxane prepolymer body, used glimmering
The quality amount ratio of luminescent material is 2~5：1：0.8~3, the gross mass of three kinds of fluorescent materials used and used with the quality of performed polymer
Amount is than being 1：10~150；Drop overlays on the LED of 365 nanometers of unencapsulated back ends (i.e. with 365 nanometers for light source back end chip afterwards
Lamp bead) device surface, dried 0.5~4 hour under the conditions of the LED component then is placed in into 45~75 DEG C.
Above-mentioned experimental method is raw materials used to be pre-dissolved copper source solvent, alkyl for copper source, higher boiling main body reaction dissolvent, low boiling
Mercaptan or aromatic thiol cladding part.Copper source can be CuCl2、Cu(Ac)2、Cu(C5H7O2)2(acetylacetone copper) etc.；Higher boiling
Main body reaction dissolvent can be dielectric constant atoleine from low to high, octadecylene, benzyl ether etc.；Low boiling is pre-dissolved copper source
Solvent can be dielectric constant hexamethylene from low to high, pentane, n-hexane, acetonitrile, methanol, ethanol, acetone, formamide,
Dimethyl sulfoxide (DMSO), water etc.；Alkyl hydrosulfide cladding part can be hexyl mercaptan, spicy thioalcohol, lauryl mercaptan, Stearyl mercaptan
Deng；Aromatic thiol cladding part can be 4- chlorothio-phenols, 4- bromo thiophenols etc..
Compared with prior art, the invention has the advantages that：
The raw material that the present invention uses all is the commercial inorganic salts that can directly buy, organic ligand and solvent, it is not necessary to
It is further to handle, proportionally directly mixed, and react room temperature and carry out, experiment is simple and safe, and has well
Repeatability, it can be mass, obtained copper cluster assembly fluorescent material has higher stability.
The present invention is using commercial inorganic copper salt as body material, compared to perovskite quantum dot and semiconductor-quantum-point material,
Copper electrodissolution is low, synthetic method is environmentally protective, cheap, is advantageous to practical application.
The present invention introduces defect in an assembling process using the reaction dissolvent of differing dielectric constant, adjusts defects count and category
Property (i.e. cosmetic bug, embed defect) it is i.e. controllable photochromic, so, subsequent assembly and regulation process, it is only necessary to according to final need
The glow color target capabilities wanted, by simply change reaction dissolvent species or proportioning i.e. can reach regulation assemble pattern and
Realize the purpose of visible region full color emission.Moreover, when different photochromic copper cluster assembly fluorescent material mutually mix unstressed configuration be quenched or
Energy transfer phenomenon occurs, and is used as luminescent layer using special ratios mixing material, you can obtain White-light LED illumination device.
Brief description of the drawings
Fig. 1：Embodiment 1 is part using spicy thioalcohol, and atoleine is higher boiling main body reaction dissolvent, and n-hexane is low boiling
Point is pre-dissolved copper source solvent, is stirred at room temperature down, and the fluorescence color of preparation is the transmission of the copper nano-cluster self assembly fluorescent material of blueness
Electron micrograph (a) and fluorescence spectrum (b), patterns of the Fig. 1 (a) for copper nano-cluster self assembly fluorescent material under microcosmic, its
It is long 800~900 nanometers to be wide 800~900 nanometers, high 45~50 nanometers of two-dimensional slice package assembly；Can be with from Fig. 1 (b)
Find out, in a length of 365nm of excitation light wave, transmitting photopeak position is in 490nm.
Fig. 2：Embodiment 2 is part using spicy thioalcohol, and atoleine is higher boiling main body reaction dissolvent, and acetonitrile is low boiling
Copper source solvent is pre-dissolved, is stirred at room temperature down, the fluorescence color of preparation is electric for the transmission of the copper nano-cluster self assembly fluorescent material of green
Sub- microphotograph (a) and fluorescence spectrum (b), patterns of the Fig. 2 (a) for copper nano-cluster self assembly fluorescent material under microcosmic, it is
It is wide 300~400 nanometers, long 800~900 nanometers, high 40~45 nanometers of two-dimensional slice package assembly；Can from Fig. 2 (b)
Go out, in a length of 365nm of excitation light wave, transmitting photopeak position is in 521nm.
Fig. 3：Embodiment 3 is part using spicy thioalcohol, and atoleine is higher boiling main body reaction dissolvent, and ethanol is low boiling
Copper source solvent is pre-dissolved, is stirred at room temperature down, the fluorescence color of preparation is the transmission of the copper nano-cluster self assembly fluorescent material of yellow green
Electron micrograph (a) and fluorescence spectrum (b), patterns of the Fig. 3 (a) for copper nano-cluster self assembly fluorescent material under microcosmic, its
It is long 900~1000 nanometers to be wide 200~300 nanometers, high 30~35 nanometers of two-dimensional slice package assembly transmission electron microscope photo；
From Fig. 3 (b) as can be seen that in a length of 365nm of excitation light wave, transmitting photopeak position is in 548nm.
Fig. 4：Embodiment 4 is part using spicy thioalcohol, and octadecylene is higher boiling main body reaction dissolvent, and ethanol is that low boiling is pre-
Molten copper source solvent, is stirred at room temperature down, and the fluorescence color of preparation is the transmitted electron of the copper nano-cluster self assembly fluorescent material of yellow
Microphotograph (a) and fluorescence spectrum (b), patterns of the Fig. 4 (a) for copper nano-cluster self assembly fluorescent material under microcosmic, it is width
It is 200~300 nanometers, long 1.2~1.4 microns, high 25~30 nanometers of two-dimensional slice package assembly transmission electron microscope photo；From Fig. 4
(b) in as can be seen that in a length of 365nm of excitation light wave, transmitting photopeak position is in 572nm.
Fig. 5：Embodiment 5 is part using spicy thioalcohol, and octadecylene is higher boiling main body reaction dissolvent, and formamide is low boiling
Copper source solvent is pre-dissolved, is stirred at room temperature down, the fluorescence color of preparation is electric for the transmission of orange copper nano-cluster self assembly fluorescent material
Sub- microphotograph (a) and fluorescence spectrum (b), patterns of the Fig. 5 (a) for copper nano-cluster self assembly fluorescent material under microcosmic, it is
It is wide 200~300 nanometers, long 2~3 microns, high 20~25 nanometers of two-dimensional slice package assembly transmission electron microscope photo；From Fig. 5 (b)
In as can be seen that in a length of 365nm of excitation light wave, transmitting photopeak position is in 590nm.
Fig. 6：Embodiment 6 is part using spicy thioalcohol, and benzyl ether is higher boiling main body reaction dissolvent, and dimethyl sulfoxide (DMSO) is low
Boiling point is pre-dissolved copper source solvent, is stirred at room temperature down, and the fluorescence color of preparation is orange-red copper nano-cluster self assembly fluorescent material
Transmission electron microscope photo (a) and fluorescence spectrum (b), shapes of the Fig. 6 (a) for copper nano-cluster self assembly fluorescent material under microcosmic
Looks, it is wide 80~100 nanometers, and long several microns to more than ten microns, high 15~20 nanometers of two-dimensional ribbon there package assembly is saturating
Penetrate electromicroscopic photograph；From Fig. 6 (b) as can be seen that in a length of 365nm of excitation light wave, transmitting photopeak position is in 642nm.
Fig. 7：Embodiment 7 is part using spicy thioalcohol, and benzyl ether is higher boiling main body reaction dissolvent, and water is pre-dissolved for low boiling
Copper source solvent, is stirred at room temperature down, and the fluorescence color of preparation shows for the transmitted electron of red copper nano-cluster self assembly fluorescent material
Micro mirror photo (a) and fluorescence spectrum (b), patterns of the Fig. 7 (a) for copper nano-cluster self assembly fluorescent material under microcosmic, it is wide by 50
~80 nanometers, long several microns to more than ten microns, high 10~15 nanometers of two-dimentional fibre-like package assembly transmission electron microscope shines
Piece；From Fig. 7 (b) as can be seen that in a length of 365nm of excitation light wave, transmitting photopeak position is in 670nm.
Fig. 8：(a), (c) and (e) is respectively to coat part using spicy thioalcohol, and atoleine is that higher boiling main body reacts molten
Agent, n-hexane are that low boiling is pre-dissolved copper source solvent；Spicy thioalcohol is cladding part, and atoleine is higher boiling main body reaction dissolvent,
Acetonitrile is that low boiling is pre-dissolved copper source solvent；Spicy thioalcohol is cladding part, and benzyl ether is higher boiling main body reaction dissolvent, and water is low boiling
Point is pre-dissolved copper source solvent, is stirred at room temperature down, the copper nano-cluster self-assembled material of preparation with dimethyl silicone polymer is compound is used as face
Color converting layer, the LED chip of 365nm back ends is the blue and green light of light emitting source preparation and the luminescent spectrum of red-light LED device.
(b), (d) and (f) is respectively chromaticity coordinates corresponding to spectrum, it was confirmed that its glow color is respectively blue and green light and feux rouges.
Fig. 9：Blue and green light is with feux rouges copper nano-cluster self-assembled material with mass ratio 2：1：With poly- two after the mixing of 0.8 ratio
Methylsiloxane is compound to be used as color conversion layer, and the LED chip of 365nm back ends is fine copper cluster white light LEDs device prepared by light emitting source
Chromaticity coordinates (b) corresponding to the luminescent spectrum (a) and spectrum of part, its chromaticity coordinates are (0.33,0.34).
Embodiment
With reference to embodiment, the present invention is further elaborated, rather than to be limited the invention with this.
Embodiment 1
200 μ L n-hexanes are added in 25mL single port bottle and dissolved with 0.06mmol CuCl2·2H2O, ultrasound make copper
Source is completely dissolved, and is added 10mL atoleines, under room temperature magnetic agitation, is added 1.2mmol spicy thioalcohol, ultrasound makes mixing equal
Even, then room temperature is kept stirring for 30min.Reacted 10mL solution is poured into 100mL centrifuge tubes, successively adds 20mL dichloromethanes
Alkane and 40mL ethanol, after shaking up, 3000r/min centrifugations 3min；Above product centrifugally operated is repeated with same steps three times, is drained
Product, you can the stable copper nano-cluster lamella assembly materials of spicy thioalcohol are obtained, as shown in figure 1, being Fluorescent peal 490nm's
Blue light fluorescent powder.
Embodiment 2
200 μ L acetonitriles are added in 25mL single port bottle and dissolved with 0.06mmol CuCl2·2H2O, ultrasound make copper source
It is completely dissolved, adds 10mL atoleines, under room temperature magnetic agitation, add 1.2mmol spicy thioalcohol, ultrasound makes mixing equal
Even, then room temperature is kept stirring for 30min.Reacted 10mL solution is poured into 100mL centrifuge tubes, successively adds 20mL dichloromethanes
Alkane and 40mL ethanol, after shaking up, 3000r/min centrifugation 3min, repeat above product centrifugally operated three times with same steps, drain
Product, you can the stable copper nano-cluster lamella assembly materials of spicy thioalcohol are obtained, as shown in Fig. 2 being Fluorescent peal 521nm's
Green light fluorescent powder.
Embodiment 3
200 μ L ethanol are added in 25mL single port bottle and dissolved with 0.06mmol CuCl2·2H2O, ultrasound make copper source
It is completely dissolved, adds 10mL atoleines, under room temperature magnetic agitation, add 1.2mmol spicy thioalcohol, ultrasound makes mixing equal
Even, then room temperature is kept stirring for 30min.Reacted 10mL solution is poured into 100mL centrifuge tubes, successively adds 20mL dichloromethanes
Alkane and 40mL ethanol, after shaking up, 3000r/min centrifugation 3min, repeat above product centrifugally operated three times with same steps, drain
Product, you can the stable copper nano-cluster lamella assembly materials of spicy thioalcohol are obtained, as shown in figure 3, being Fluorescent peal 548nm's
Yellowish green emitting phosphor.
Embodiment 4
200 μ L ethanol are added in 25mL single port bottle and dissolved with 0.06mmol CuCl2·2H2O, ultrasound make copper source
It is completely dissolved, adds 10mL octadecylenes, under room temperature magnetic agitation, add 1.2mmol spicy thioalcohol, ultrasound makes to be well mixed,
Then room temperature is kept stirring for 30min.Reacted 10mL solution is poured into 100mL centrifuge tubes, successively adds 20mL dichloromethane
With 40mL ethanol, after shaking up, 3000r/min centrifugation 3min, repeat above product centrifugally operated three times with same steps, drain production
Product, you can obtain the stable copper nano-cluster lamella assembly materials of spicy thioalcohol, as shown in figure 4, for Fluorescent peal 572nm Huang
Emitting phosphor.
Embodiment 5
200 μ L formamides are added in 25mL single port bottle and dissolved with 0.06mmol CuCl2·2H2O, ultrasound make copper
Source is completely dissolved, and is added 10mL octadecylenes, under room temperature magnetic agitation, is added 1.2mmol spicy thioalcohol, ultrasound makes mixing equal
Even, then room temperature is kept stirring for 30min.Reacted 10mL solution is poured into 100mL centrifuge tubes, successively adds 20mL dichloromethanes
Alkane and 40mL ethanol, after shaking up, 3000r/min centrifugation 3min, repeat above product centrifugally operated three times with same steps, drain
Product, you can the stable copper nano-cluster lamella assembly materials of spicy thioalcohol are obtained, as shown in figure 5, being Fluorescent peal 590nm's
Orange light phosphor powder.
Embodiment 6
200 μ L dimethyl sulfoxide (DMSO)s are added in 25mL single port bottle and dissolved with 0.06mmol CuCl2·2H2O, ultrasound
Copper source is completely dissolved, 10mL benzyl ether is added, under room temperature magnetic agitation, adds 1.2mmol spicy thioalcohol, ultrasound makes mixing
Uniformly, then room temperature is kept stirring for 30min.Reacted 10mL solution is poured into 100mL centrifuge tubes, successively adds 20mL dichloros
Methane and 40mL ethanol, after shaking up, 3000r/min centrifugation 3min, repeat above product centrifugally operated three times with same steps, take out
Dryed product, you can the stable copper nano-cluster band assembly materials of spicy thioalcohol are obtained, as shown in fig. 6, being Fluorescent peal in 642nm
Orange red emitting phosphor.
Embodiment 7
200 μ L water are added in 25mL single port bottle and dissolved with 0.06mmol CuCl2·2H2O, ultrasound make copper source complete
Fully dissolved, 10mL benzyl ether is added, under room temperature magnetic agitation, adds 1.2mmol spicy thioalcohol, ultrasound makes to be well mixed, so
Room temperature is kept stirring for 30min afterwards.Reacted 10mL solution is poured into 100mL centrifuge tubes, successively add 20mL dichloromethane and
40mL ethanol, after shaking up, 3000r/min centrifugation 3min, repeat above product centrifugally operated three times with same steps, drain production
Product, you can the stable copper nano-cluster fibre-like assembly materials of spicy thioalcohol are obtained, as shown in fig. 7, being Fluorescent peal in 670nm
Red light fluorescent powder.
Embodiment 8
By the blue light copper cluster lamella assembly materials (glow peak 490nm) that the spicy thioalcohol after centrifugal drying is stable, green glow copper
Cluster lamella assembly materials (glow peak 521nm), and feux rouges copper cluster fibre-like assembly materials (glow peak 671nm) are ground into powder
End.
Each 19mg of fluorescent material and a 3 kinds of assembly materials quality for taking this 3 kinds of peak positions are respectively 10mg, 5mg, 4mg
Mixed fluorescent powder, it is compound with the prepolymer of 300mg dimethyl silicone polymers respectively, be then respectively coated on unencapsulated 4
Back end is in 365nm LED chip, is placed in 1h in 65 DEG C of baking ovens, you can it is respectively blue, green to obtain packaged glow color
The LED light source of color, red and white, respectively as shown in Figure 8 and Figure 9.
Claims (5)
- A kind of 1. preparation method of the full color emission copper cluster assembly fluorescent material of solvent regulation and control, it is characterised in that：Copper source is pre- First it is fully immersed into low boiling to be pre-dissolved in the solvent of copper source, 2~5min of ultrasound, it is molten that above-mentioned solution then is dissolved in into the reaction of higher boiling main body In agent, it is 1 that low boiling, which is pre-dissolved copper source solvent and the volumetric usage ratio of higher boiling main body reaction dissolvent,：10~50, copper source is in low boiling The mass concentration that point is pre-dissolved in the solvent of copper source is 10~50%；Room temperature adds alkyl hydrosulfide or aromatic thiol cladding under magnetic agitation The mole dosage ratio in part, part and copper source is 5~30：1,2~5min of ultrasound is allowed to well mixed, then stirs at room temperature 2min~1h, the white suspension centrifugal purification that will be obtained；Alkyl sulfide is obtained after obtained centrifugation product vacuum is drained again The full color emission copper cluster assembly fluorescent material of alcohol or aromatic thiol cladding part stabilization.
- 2. a kind of preparation method of the full color emission copper cluster assembly fluorescent material of solvent regulation and control as claimed in claim 1, its It is characterised by：Centrifugal purification is that dichloromethane and ethanol are added into white suspension, after shaking up, 2000~5000r/min from 2~5min of the heart, the volumetric usage ratio of white suspension, dichloromethane and ethanol is 1：1~3：2~6.
- 3. a kind of preparation method of the full color emission copper cluster assembly fluorescent material of solvent regulation and control as claimed in claim 1, its It is characterised by：Copper source is CuCl2、Cu(Ac)2Or Cu (C5H7O2)2；Higher boiling main body reaction dissolvent be atoleine, octadecylene or Benzyl ether；It is hexamethylene, pentane, n-hexane, acetonitrile, methanol, ethanol, acetone, formamide, two that low boiling, which is pre-dissolved copper source solvent, Methyl sulfoxide or water；Alkyl hydrosulfide cladding part is hexyl mercaptan, spicy thioalcohol, lauryl mercaptan or Stearyl mercaptan；Fragrance Mercaptan cladding part is 4- chlorothio-phenols or 4- bromo thiophenols.
- A kind of 4. full color emission copper cluster assembly fluorescent material of solvent regulation and control, it is characterised in that：It is to be appointed by claims 1 to 3 Method described in what one is prepared.
- 5. a kind of full color emission copper cluster assembly fluorescent material of solvent regulation and control as claimed in claim 1 is to prepare fine copper cluster white Application in light LED illumination device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710579460.8A CN107338042B (en) | 2017-07-17 | 2017-07-17 | Full color emission copper cluster assembly fluorescent material, preparation method and its application in white light LED part of solvent regulation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710579460.8A CN107338042B (en) | 2017-07-17 | 2017-07-17 | Full color emission copper cluster assembly fluorescent material, preparation method and its application in white light LED part of solvent regulation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107338042A true CN107338042A (en) | 2017-11-10 |
| CN107338042B CN107338042B (en) | 2019-07-09 |
Family
ID=60218716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710579460.8A Expired - Fee Related CN107338042B (en) | 2017-07-17 | 2017-07-17 | Full color emission copper cluster assembly fluorescent material, preparation method and its application in white light LED part of solvent regulation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107338042B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909295A (en) * | 2020-07-01 | 2020-11-10 | 北京大学深圳研究生院 | Preparation method and application of photosensitization material |
| CN112080275A (en) * | 2020-09-21 | 2020-12-15 | 吉林大学 | Color temperature adjustable white light emitting copper cluster assembly fluorescent material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820106A (en) * | 2014-02-24 | 2014-05-28 | 东南大学 | Green synthetic method of fluorescence copper nano-cluster, and application of fluorescence copper nano-cluster |
| CN104807795A (en) * | 2015-05-06 | 2015-07-29 | 江南大学 | Fast preparation method of biological affinity copper nanometer cluster |
| CN105304799A (en) * | 2015-10-16 | 2016-02-03 | 吉林大学 | Method for preparing LEDs with different light colors based on metal nano-cluster packaging material |
| CN105602554A (en) * | 2016-03-09 | 2016-05-25 | 吉林大学 | Au-doped copper nano-cluster self-assembly fluorescent material, preparing method and application thereof to LED packaging |
| CN106590635A (en) * | 2016-12-07 | 2017-04-26 | 吉林大学 | Yellow-light or red-light copper cluster assembly fluorescent material, and preparation method and application thereof in preparation of pure copper cluster white-light LED device |
-
2017
- 2017-07-17 CN CN201710579460.8A patent/CN107338042B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820106A (en) * | 2014-02-24 | 2014-05-28 | 东南大学 | Green synthetic method of fluorescence copper nano-cluster, and application of fluorescence copper nano-cluster |
| CN104807795A (en) * | 2015-05-06 | 2015-07-29 | 江南大学 | Fast preparation method of biological affinity copper nanometer cluster |
| CN105304799A (en) * | 2015-10-16 | 2016-02-03 | 吉林大学 | Method for preparing LEDs with different light colors based on metal nano-cluster packaging material |
| CN105602554A (en) * | 2016-03-09 | 2016-05-25 | 吉林大学 | Au-doped copper nano-cluster self-assembly fluorescent material, preparing method and application thereof to LED packaging |
| CN106590635A (en) * | 2016-12-07 | 2017-04-26 | 吉林大学 | Yellow-light or red-light copper cluster assembly fluorescent material, and preparation method and application thereof in preparation of pure copper cluster white-light LED device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909295A (en) * | 2020-07-01 | 2020-11-10 | 北京大学深圳研究生院 | Preparation method and application of photosensitization material |
| CN111909295B (en) * | 2020-07-01 | 2022-07-26 | 北京大学深圳研究生院 | Preparation method and application of photosensitization material |
| CN112080275A (en) * | 2020-09-21 | 2020-12-15 | 吉林大学 | Color temperature adjustable white light emitting copper cluster assembly fluorescent material and preparation method thereof |
| CN112080275B (en) * | 2020-09-21 | 2021-08-27 | 吉林大学 | Color temperature adjustable white light emitting copper cluster assembly fluorescent material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107338042B (en) | 2019-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Polymer-assisted self-assembly of multicolor carbon dots as solid-state phosphors for fabrication of warm, high-quality, and temperature-responsive white-light-emitting devices | |
| Su et al. | Highly luminescent water-soluble AgInS2/ZnS quantum dots-hydrogel composites for warm white LEDs | |
| Wang et al. | A self-quenching-resistant carbon dots powder with tunable solid-state fluorescence and their applications in light-emitting diodes and fingerprints detection | |
| CN105304799B (en) | A kind of method that different glow color LED are prepared based on metal nanometre cluster encapsulating material | |
| CN107338042B (en) | Full color emission copper cluster assembly fluorescent material, preparation method and its application in white light LED part of solvent regulation | |
| CN113025316B (en) | High-quantum-yield copper nanocluster fluorescent nanoflower, preparation method thereof and application thereof in LED | |
| CN106675550A (en) | Perovskite quantum dot gel and preparation method thereof | |
| CN105602554B (en) | Copper nano-cluster self assembly fluorescent material, preparation method and its application in LED encapsulation of gold doping | |
| CN105802614A (en) | Preparation method of quantum dot and quantum dot prepared by same | |
| CN106947485A (en) | A kind of synthetic method of quantum dot photonic crystal laminated film | |
| CN109370263A (en) | A kind of preparation method of panchromatic varistructure chromogenic materials | |
| CN109876830A (en) | A kind of regulation BiOX (X=Cl, Br, I) the photochemical catalyst preparation of multicomponent solvent and application | |
| CN102634336A (en) | Luminescence-adjustable ligand-free cadmium sulfide semiconductor quantum dot and preparation method thereof | |
| Mukherjee et al. | Ag-doped ZnInS/ZnS core/shell quantum dots for display applications | |
| CN103834408A (en) | Preparation method of water phase CdTe/CdSe core-shell quantum dots for rapid fingerprint appearance | |
| Jiang et al. | Cd-free Cu–Zn–In–S/ZnS quantum dots@ SiO2 multiple cores nanostructure: Preparation and application for white LEDs | |
| CN106590635B (en) | Yellow light or feux rouges copper cluster assembly fluorescent material, preparation method and its preparing the application in fine copper cluster white light LED part | |
| CN107552809B (en) | A kind of synthetic method for the color controllable fluorescence gold nanoclusters that silver is adjusted | |
| CN110408386B (en) | Indium sulfide silver quantum dot changing from green light to red light and one-step synthesis method and application thereof | |
| CN112940719A (en) | Preparation of carboxylated CuInS with chemiluminescence characteristic2Universal method for @ ZnS nano material | |
| Ding et al. | Free inert gas protection, low temperature, non-injection synthesis of CdS and doped quantum dots for efficient white light-emitting diodes | |
| CN101704507B (en) | Method for synthesizing quantum dot with core-shell-shell structure in aqueous phase | |
| CN107805495A (en) | The preparation method of high brightness zinc-manganese sulfide nano-phosphor | |
| CN107629182B (en) | A kind of polysiloxanes-benzoxazinyl- light-emitting film and its application on UV-LED lamp | |
| CN100523119C (en) | Aqueous phase preparation method of water-soluble core/shell-type CdTe/Cd(OH)2 nano-crystal |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190709 Termination date: 20200717 |