CN106590635B - 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 - Google Patents
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 Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 78
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 32
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 18
- 238000005253 cladding Methods 0.000 claims description 10
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical group C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- OKIHXNKYYGUVTE-UHFFFAOYSA-N 4-Fluorothiophenol Chemical compound FC1=CC=C(S)C=C1 OKIHXNKYYGUVTE-UHFFFAOYSA-N 0.000 claims description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- FTBCOQFMQSTCQQ-UHFFFAOYSA-N 4-bromobenzenethiol Chemical compound SC1=CC=C(Br)C=C1 FTBCOQFMQSTCQQ-UHFFFAOYSA-N 0.000 claims description 5
- NIFAOMSJMGEFTQ-UHFFFAOYSA-N 4-methoxybenzenethiol Chemical compound COC1=CC=C(S)C=C1 NIFAOMSJMGEFTQ-UHFFFAOYSA-N 0.000 claims description 5
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 claims description 5
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011435 rock Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005286 illumination Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000009877 rendering Methods 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 description 16
- 238000001338 self-assembly Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 9
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 8
- 230000005284 excitation Effects 0.000 description 8
- 238000002189 fluorescence spectrum Methods 0.000 description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920005573 silicon-containing polymer Polymers 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- GKQXPTHQTXCXEV-UHFFFAOYSA-N (4-chlorophenyl)methanethiol Chemical compound SCC1=CC=C(Cl)C=C1 GKQXPTHQTXCXEV-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 description 1
- -1 aliphatic mercapto Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- FJYLYGYKFHDFEW-UHFFFAOYSA-N benzenethiol;bromobenzene Chemical compound SC1=CC=CC=C1.BrC1=CC=CC=C1 FJYLYGYKFHDFEW-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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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
- H01L33/502—Wavelength conversion materials
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- H—ELECTRICITY
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- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
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- Microelectronics & Electronic Packaging (AREA)
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- Optics & Photonics (AREA)
- Luminescent Compositions (AREA)
Abstract
Yellow light or feux rouges copper cluster assembly fluorescent material, preparation method and its application in fine copper cluster white light LED part is being prepared, is belonging to White-light LED illumination technical field.The present invention uses colloidal solution one kettle way, utilize high boiling solvent, aromatic series and aliphatic sulfydryl coat ligand, by simply heating, the two-dimensional ribbon there assembly fluorescent material of the stable transmitting yellow light or feux rouges assembled by copper cluster is obtained, can reach the regulation to fluorescent emission peak position by simply regulating and controlling ligand structure i.e..The assembly method of manufacturing fluorescent material is simple, quickly, can mass production, low raw-material cost, technique are pollution-free, and obtained material brightness and stability are all improved, and when premixing white light, unstressed configuration is quenched or energy transfer phenomenon occurs, therefore the assembly fluorescent material can be applied to the White-light LED illumination field of high color rendering index (CRI).
Description
Technical field
The invention belongs to White-light LED illumination technical fields, and in particular to coat ligand using aromatic series and aliphatic sulfydryl
The yellow light or feux rouges copper cluster assembly fluorescent material of preparation, preparation method and its preparing answering in fine copper cluster white light LED part
With.
Background technique
Super-small metal nanometre cluster is since it is with hyperfine structure, hypotoxicity, good bio-compatibility, big Si Tuo
Ke Si displacement becomes the potential fluorescent material of tool.The research of gold and silver fluorescence nano cluster is increasingly mature, but noble metal
High cost limit it in the process of commercial applications.And copper cluster luminous peak position focused mostly on before yellow light, and brightness with
Stability is poor.From the aspect of functionization, is highlighted and stable cheap nanocluster fluorescence material is visited as each side
The hot spot of rope.
The white light parts constructed by pure metal cluster often have fluorescent quenching or energy transfer situation in raw material premix, give work
Skill brings difficulty.
Based on the above reasons, we construct copper cluster assembly phosphor using aromatic series and aliphatic sulfydryl cladding ligand
Material, and it is realized in the transmitting of yellow light and red light district, and can change glow peak by simply changing ligand structure
Position.Assembling enhances brightness and stability, and assembly materials do not have fluorescent quenching and energy when premix constructs white light
Transfer phenomena is based on this, is blended using obtained yellow light, red light material with blue light copper clustered materials before, has constructed and be based on fine copper
The white light parts of cluster assembly materials.This research has very big value to the development based on metal cluster white-light illuminating field.
Summary of the invention
The object of the present invention is to provide a kind of yellow lights or feux rouges prepared using aromatic series and aliphatic sulfydryl cladding ligand
Copper cluster assembly fluorescent material, preparation method and its application in the fine copper cluster white light LED part for preparing high color rendering index (CRI).
The assembly fluorescent material emphasis is to coat ligand using aromatic mercapto group, and the energy band for the copper cluster assembly that narrows makes
It shines and concentrates on red light district.It, can mass production, cost of material since the assembly method of manufacturing fluorescent material is simple, quick
It is cheap, technique is pollution-free, and obtained material brightness and stability are all improved, and noenergy turns when premixing white light
It moves, therefore the assembly fluorescent material can be applied to the White-light LED illumination field of high color rendering index (CRI).
The present invention uses colloidal solution one kettle way, and using high boiling solvent, aromatic series and aliphatic sulfydryl coat ligand, leads to
Simple heat treatment is crossed, the two-dimensional ribbon there assembly fluorescence of the stable transmitting yellow light or feux rouges assembled by copper cluster is obtained
Material can reach the regulation to fluorescent emission peak position by simply regulating and controlling ligand structure i.e..
Specifically, the preparation method of yellow light or feux rouges copper cluster assembly fluorescent material of the present invention, step is such as
Under:
Copper source is dissolved in high boiling solvent, copper source mass concentration is 1~5%, and aromatic series is added under room temperature magnetic agitation
Or aliphatic sulfydryl coats ligand, the molar ratio of ligand and copper source is 5~25:1, and ultrasound is allowed to uniformly mixed, at 45~90 DEG C
0.5~6h of stirring in water bath, then cools to room temperature；By obtained yellowish suspension and chloroform, acetone 1:2:4 by volume
Ratio mixing, rock uniformly after with 6000~8000r/min be centrifuged 5~10min, outwell supernatant；It is produced again to centrifugation gained
The chloroform and acetone solvent of above-mentioned equal volume are added in object, repeats above centrifugation centrifugally operated 2~3 times, obtained and produces
Aromatic series or the stable two-dimensional ribbon there assembling assembled by copper cluster of aliphatic sulfydryl cladding ligand can be obtained in object after draining
Body fluorescent material.By change sulfydryl coat ligand structure, can be obtained yellow light or red light district difference transmitting peak position yellow light or
Feux rouges copper cluster assembly fluorescent material.
Preparation based on fine copper cluster assembly fluorescent material white light LED part: by blue light copper cluster assembly fluorescent material
(Wu,Z.；Liu,J.；Gao,Y.；Liu,H.；Li,T.；Zou,H.；Wang,Z,；Zhang,K.；Wang,Y.；Zhang,H.；et
al.Assembly-Induced Enhancement of Cu Nanoclusters Luminescence with
Mechanochromic Property.J.Am.Chem.Soc.2015,137,12906.) and yellow light copper cluster assembly phosphor
Material and the feux rouges copper cluster assembly fluorescent material of different transmitting peak positions are uniformly mixed with the prepolymer of dimethyl silicone polymer, used
The quality amount ratio of fluorescent material be 2:0.5:0.9:0.9:1.2, the gross mass of a variety of fluorescent materials used and with prepolymer
Quality amount ratio is 1:50~200；The LED that drop overlays on 365 nanometers of unencapsulated back ends later (is carried on the back with 365 nanometers for light source
The lamp bead of bottom chip) device surface, dries 1~5 hour under the conditions of the LED component is then placed in 50~85 DEG C.
Above-mentioned experimental method is raw materials used to coat ligand and aliphatic mercapto for copper source, high boiling solvent, aromatic mercapto group
Base coats ligand.Copper source can be CuCl2、CuSO4、Cu(NO3)2Deng；High boiling solvent can be benzyl ether, atoleine etc.
Deng；Aromatic mercapto group cladding ligand can be HSC6H4F、HSC6H4Cl、HSC6H4Br、HSC6H4CH3、HSC6H4OCH3Deng different right
The benzenethiol that position replaces.Aliphatic sulfydryl cladding ligand can be 4- chloro benzyl mercaptan, cyclohexylmercaptan, mercaptopropionic acid etc..
Compared with prior art, the present invention has the advantage that
The raw material that the present invention uses all is the inorganic salts that commercially can directly buy, organic ligand and solvent, is not needed
It is further processed, is proportionally directly mixed, and reaction temperature is low, experiment is simple and safe, and has good heavy
Renaturation, can large production, obtained yellow light or feux rouges copper cluster assembly fluorescent material stability are preferable.
The present invention is with commercial CuCl2、CuSO4、Cu(NO3)2The raw material Deng based on, compared to organic and semiconductor material, copper
Reserves are big, cheap, and toxicity is low, are conducive to industrial applications.Moreover, unstressed configuration is quenched when different photochromic fluorescent powders mutually mix
Or energy transfer phenomenon occurs, the White-light LED illumination of high color rendering index (CRI) can be obtained as light conversion layer in special ratios mixing material
Device.
Detailed description of the invention
Fig. 1: embodiment 1 is the copper nano-cluster self assembly fluorescence of yellow using the fluorescence color of 4- fluoro thiophenol ligand preparation
The transmission electron microscope photo (a) and fluorescence spectrum (b) of material, Fig. 1 (a) are under copper nano-cluster self assembly fluorescent material is microcosmic
Pattern, to be 100 nanometers wide, long several microns to more than ten microns not equal band package assembly transmission electron microscope photos；From Fig. 1
(b) in as can be seen that in a length of 365nm of excitation light wave, emit photopeak position in 548nm.
Fig. 2: embodiment 2 is red copper nano-cluster self assembly fluorescence using the fluorescence color of 4- chlorothio-phenol ligand preparation
The transmission electron microscope photo (a) and fluorescence spectrum (b) of material, Fig. 2 (a) are under copper nano-cluster self assembly fluorescent material is microcosmic
Pattern, to be 100 nanometers wide, long several microns to more than ten microns not equal band package assembly transmission electron microscope photos；From Fig. 2
(b) in as can be seen that in a length of 365nm of excitation light wave, emit photopeak position in 646nm.
Fig. 3: embodiment 3 is red copper nano-cluster self assembly fluorescence using the fluorescence color of 4- bromo thiophenol ligand preparation
The transmission electron microscope photo (a) and fluorescence spectrum (b) of material, Fig. 3 (a) are under copper nano-cluster self assembly fluorescent material is microcosmic
Pattern, to be 100 nanometers wide, long several microns to more than ten microns not equal band package assembly transmission electron microscope photos；From Fig. 3
(b) in as can be seen that in a length of 365nm of excitation light wave, emit photopeak position in 659nm.
Fig. 4: embodiment 4 is that red copper nano-cluster self assembly is glimmering using the fluorescence color of 4- methylbenzene phenyl-sulfhydrate ligand preparation
The transmission electron microscope photo (a) and fluorescence spectrum (b) of luminescent material, Fig. 4 (a) are that copper nano-cluster self assembly fluorescent material is microcosmic
Under pattern, to be 100 nanometers wide, long several microns to more than ten microns not equal band package assembly transmission electron microscope photos；From Fig. 4
(b) in as can be seen that in a length of 365nm of excitation light wave, emit photopeak position in 677nm.
Fig. 5: embodiment 5 is red copper nano-cluster self assembly using the fluorescence color of 4- methoxybenzenethiol ligand preparation
The transmission electron microscope photo (a) and fluorescence spectrum (b) of fluorescent material, Fig. 5 (a) are that copper nano-cluster self assembly fluorescent material is micro-
Pattern under seeing is 100 nanometers wide, long several microns to the more than ten microns band package assembly transmission electron microscope photos not waited；From
In Fig. 5 (b) as can be seen that in a length of 365nm of excitation light wave, emit photopeak position in 698nm.
Fig. 6: embodiment 6 is the copper nano-cluster self assembly fluorescence of yellow using the fluorescence color of 4- chloro benzyl mercaptan ligand preparation
The transmission electron microscope photo (a) and fluorescence spectrum (b) of material, Fig. 6 (a) are under copper nano-cluster self assembly fluorescent material is microcosmic
Pattern, to be 350 nanometers wide, long 500 nanometers to 800 nanometers not equal flake-assembly mode structure for transmission electron microscope photos；From Fig. 6
(b) in as can be seen that in a length of 365nm of excitation light wave, emit photopeak position in 558nm.
Fig. 7: embodiment 7 is the copper nano-cluster self assembly phosphor of yellow using the fluorescence color of cyclohexylmercaptan ligand preparation
The transmission electron microscope photo (a) and fluorescence spectrum (b) of material, Fig. 7 (a) are under copper nano-cluster self assembly fluorescent material is microcosmic
Pattern is 200 nanometers to 300 nanometers wide, long several microns to the more than ten microns band package assembly transmission electron microscope photos not waited；
From Fig. 7 (b) as can be seen that in a length of 365nm of excitation light wave, emit photopeak position in 569nm.
Fig. 8: embodiment 8 is the copper nano-cluster self assembly phosphor of yellow using the fluorescence color of mercaptopropionic acid ligand preparation
The transmission electron microscope photo (a) and fluorescence spectrum (b) of material, Fig. 8 (a) are under copper nano-cluster self assembly fluorescent material is microcosmic
Pattern is 250 nanometers wide, long several microns to the more than ten microns ribbon package assembly transmission electron microscope photos not waited；From Fig. 8
(b) in as can be seen that in a length of 365nm of excitation light wave, emit photopeak position in 500nm.
Fig. 9: (a), (c), (e), (g) and (i) is respectively to utilize ligand lauryl mercaptan, 4- fluoro thiophenol, 4- bromobenzene
Thiophenol, the copper nano-cluster self-assembled material and dimethyl silicone polymer of 4- methylbenzene phenyl-sulfhydrate and 4- methoxybenzenethiol cladding are compound
As color conversion layer, the LED chip of 365nm back end is the blue light of light emitting source preparation, yellow light, and the feux rouges of different transmitting peak positions
The luminescent spectrum of LED component.It (b), (d), (f), (h) is respectively the corresponding chromaticity coordinates of spectrum with (j), it was confirmed that its luminescent color
The respectively feux rouges of blue light, yellow light and different transmitting peak positions.
Figure 10: the copper nano-cluster self-assembled material of different ligands cladding is mixed with mass ratio 2/0.5/0.9/0.9/1.2 ratio
Compound as color conversion layer with dimethyl silicone polymer after conjunction, the LED chip of 365nm back end is the fine copper cluster of light emitting source preparation
The corresponding chromaticity coordinates (b) of luminescent spectrum (a) and spectrum of white light LED part.Its colour rendering index be 86, chromaticity coordinates be (0.32,
0.32), colour temperature 6157K.
Specific embodiment
Below with reference to embodiment, the present invention is further elaborated, rather than to be limited the invention with this.
Embodiment 1
6mL benzyl ether is added in the beaker of 20mL, and dissolved with the CuCl of 0.04mmol2·2H2O is stirred in room temperature magnetic force
It mixes down, the 4- fluoro thiophenol of 0.9mmol is added, ultrasound makes to be uniformly mixed, and then 50 DEG C of water-baths are kept stirring 1h, is cooled to room temperature.
6mL solution after reaction pours into 50mL centrifuge tube, and 12mL chloroform and 24mL acetone, after shaking up, 6000r/ is successively added
Min is centrifuged 5min, repeats the above purifying products operation three times with same steps, drains product, it is steady that 4- fluoro thiophenol can be obtained
Fixed copper nano-cluster assembly materials, as shown in Figure 1, being yellow fluorescent powder of the Fluorescent peal in 548nm.
Embodiment 2
6mL benzyl ether is added in the beaker of 20mL, and dissolved with the CuCl of 0.04mmol2·2H2O is stirred in room temperature magnetic force
It mixes down, the 4- chlorothio-phenol of 0.9mmol is added, ultrasound makes to be uniformly mixed, and then 50 DEG C of water-baths are kept stirring 1h, is cooled to room temperature.
6mL solution after reaction pours into 50mL centrifuge tube, and 12mL chloroform and 24mL acetone, after shaking up, 6000r/ is successively added
Min is centrifuged 5min, repeats the above purifying products operation three times with same steps, drains product, it is steady that 4- chlorothio-phenol can be obtained
Fixed copper nano-cluster assembly materials, as shown in Fig. 2, being red light fluorescent powder of the Fluorescent peal in 646nm.
Embodiment 3
6mL benzyl ether is added in the beaker of 20mL, and dissolved with the CuCl of 0.04mmol2·2H2O is stirred in room temperature magnetic force
It mixes down, the 4- bromo thiophenol of 0.9mmol is added, ultrasound makes to be uniformly mixed, and then 50 DEG C of water-baths are kept stirring 1h, is cooled to room temperature.
6mL solution after reaction pours into 50mL centrifuge tube, and 12mL chloroform and 24mL acetone, after shaking up, 6000r/ is successively added
Min is centrifuged 5min, repeats the above purifying products operation three times with same steps, drains product, it is steady that 4- bromo thiophenol can be obtained
Fixed copper nano-cluster assembly materials, as shown in figure 3, being red light fluorescent powder of the Fluorescent peal in 659nm.
Embodiment 4
6mL benzyl ether is added in the beaker of 20mL, and dissolved with the CuCl of 0.04mmol2·2H2O is stirred in room temperature magnetic force
It mixes down, the 4- methylbenzene phenyl-sulfhydrate of 0.9mmol is added, ultrasound makes to be uniformly mixed, and then 50 DEG C of water-baths are kept stirring 1h, is cooled to room
Temperature.6mL solution after reaction pours into 50mL centrifuge tube, and 12mL chloroform and 24mL acetone is successively added, after shaking up,
6000r/min is centrifuged 5min, repeats the above purifying products operation three times with same steps, drains product, 4- methyl can be obtained
The stable copper nano-cluster assembly materials of benzenethiol, as shown in figure 4, being red light fluorescent powder of the Fluorescent peal in 677nm.
Embodiment 5
6mL benzyl ether is added in the beaker of 20mL, and dissolved with the CuCl of 0.04mmol2·2H2O is stirred in room temperature magnetic force
It mixes down, the 4- methoxybenzenethiol of 0.9mmol is added, ultrasound makes to be uniformly mixed, and then 50 DEG C of water-baths are kept stirring 1h, is cooled to room
Temperature.6mL solution after reaction pours into 50mL centrifuge tube, and 12mL chloroform and 24mL acetone is successively added, after shaking up,
6000r/min is centrifuged 5min, repeats the above purifying products operation three times with same steps, drains product, 4- methoxy can be obtained
The stable copper nano-cluster assembly materials of base benzenethiol, as shown in figure 5, being red light fluorescent powder of the Fluorescent peal in 698nm.
Embodiment 6
6mL benzyl ether is added in the beaker of 20mL, and dissolved with the CuCl of 0.04mmol2·2H2O is stirred in room temperature magnetic force
It mixes down, the 4- benzyl chloride thiophenol of 0.9mmol is added, ultrasound makes to be uniformly mixed, and then 50 DEG C of water-baths are kept stirring 1h, is cooled to room temperature.
6mL solution after reaction pours into 50mL centrifuge tube, and 12mL chloroform and 24mL acetone, after shaking up, 6000r/ is successively added
Min is centrifuged 5min, repeats the above purifying products operation three times with same steps, drains product, it is steady that 4- benzyl chloride thiophenol can be obtained
Fixed copper nano-cluster assembly materials, as shown in fig. 6, being yellow fluorescent powder of the Fluorescent peal in 558nm.
Embodiment 7
6mL benzyl ether is added in the beaker of 20mL, and dissolved with the CuCl of 0.04mmol2·2H2O is stirred in room temperature magnetic force
It mixes down, the cyclohexylmercaptan of 0.9mmol is added, ultrasound makes to be uniformly mixed, and then 50 DEG C of water-baths are kept stirring 1h, is cooled to room temperature.Instead
6mL solution after answering pours into 50mL centrifuge tube, and 12mL chloroform and 24mL acetone, after shaking up, 6000r/min is successively added
It is centrifuged 5min, the above purifying products operation is repeated three times with same steps, drains product, the stable copper of cyclohexylmercaptan can be obtained
Nano-cluster assembly materials, as shown in fig. 7, being yellow fluorescent powder of the Fluorescent peal in 569nm.
Embodiment 8
6mL benzyl ether is added in the beaker of 20mL, and dissolved with the CuCl of 0.04mmol2·2H2O is stirred in room temperature magnetic force
It mixes down, the mercaptopropionic acid of 0.9mmol is added, ultrasound makes to be uniformly mixed, and then 50 DEG C of water-baths are kept stirring 1h, is cooled to room temperature.Instead
6mL solution after answering pours into 50mL centrifuge tube, and 12mL chloroform and 24mL acetone, after shaking up, 6000r/min is successively added
It is centrifuged 5min, the above purifying products operation is repeated three times with same steps, drains product, the stable copper of mercaptopropionic acid can be obtained
Nano-cluster assembly materials, as shown in figure 8, being yellow fluorescent powder of the Fluorescent peal in 500nm.
Embodiment 9
By copper cluster assembly materials (the glow peak 490nm, Wu, Z. that the lauryl mercaptan after centrifugal drying is stable；Liu,
J.；Gao,Y.；Liu,H.；Li,T.；Zou,H.；Wang,Z,；Zhang,K.；Wang,Y.；Zhang,H.；et
al.Assembly-Induced Enhancement of Cu Nanoclusters Luminescence with
Mechanochromic Property.J.Am.Chem.Soc.2015,137,12906.), the stable copper cluster group of 4- fluoro thiophenol
It fills body material (glow peak 548nm), the stable copper cluster assembly materials (glow peak 659nm) of 4- bromo thiophenol, 4- methylbenzene sulphur
The stable copper cluster assembly materials (glow peak 677nm) of phenol, the stable copper cluster assembly materials (glow peak of 4- methoxybenzenethiol
698nm) it is ground into a powder.
Take each 16.5mg of the fluorescent powder of this 5 kinds of peak positions and a 5 kinds of assembly materials quality be respectively 6mg, 1.5mg,
The mixed fluorescent powder of 2.7mg, 2.7mg, 3.6mg, it is compound with the prepolymer of 250mg dimethyl silicone polymer respectively, then distinguish
In the LED chip for being 365nm coated in 6 unencapsulated back ends, it is placed in 2h in 60 DEG C of baking ovens, packaged shine can be obtained
Color is respectively the LED light source of blue, yellow, the red of different transmitting peak positions and white, as shown in Figure 9 and Figure 10 respectively.
Claims (5)
1. the preparation method of a kind of yellow light or feux rouges copper cluster assembly fluorescent material, it is characterised in that: be copper source is dissolved in it is high boiling
In point solvent, the mass concentration of copper source is 1~5%, and aromatic series is added under room temperature magnetic agitation or aliphatic sulfydryl coats ligand,
The molar ratio of ligand and copper source is 5~25:1, and ultrasound is allowed to uniformly mixed, and 0.5~6h of stirring in water bath, then cold at 45~90 DEG C
But to room temperature；By obtained yellowish suspension and chloroform, acetone by volume 1:2:4 ratio mix, rock uniformly after
It is centrifuged 5~10min with 6000~8000r/min, outwells supernatant；Above-mentioned equal volume is added into centrifugation products therefrom again
Chloroform and acetone solvent repeat above centrifugally operated 2~3 times, obtain virtue after finally draining obtained centrifugation product
Fragrant race or the stable two-dimensional ribbon there yellow light assembled by copper cluster of aliphatic sulfydryl cladding ligand or feux rouges copper cluster assembly are glimmering
Luminescent material；The aliphatic sulfydryl cladding ligand is cyclohexylmercaptan or mercaptopropionic acid；The aromatic mercapto group cladding ligand is 4-
Fluoro thiophenol, 4- chlorothio-phenol, 4- bromo thiophenol, 4- methylbenzene phenyl-sulfhydrate or 4- methoxybenzenethiol.
2. the preparation method of a kind of yellow light as described in claim 1 or feux rouges copper cluster assembly fluorescent material, it is characterised in that:
Copper source is CuCl2、CuSO4Or Cu (NO3)2。
3. the preparation method of a kind of yellow light as described in claim 1 or feux rouges copper cluster assembly fluorescent material, it is characterised in that:
High boiling solvent is benzyl ether or atoleine.
4. a kind of yellow light or feux rouges copper cluster assembly fluorescent material, it is characterised in that: be by any one of claims 1 to 3 institute
The method stated is prepared.
5. yellow light as claimed in claim 4 or feux rouges copper cluster assembly fluorescent material are in preparing fine copper cluster white light LED part
Using.
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