CN106978176A - A kind of yellow fluorescent powder and preparation method and its application in luminescent device - Google Patents
A kind of yellow fluorescent powder and preparation method and its application in luminescent device Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 230000005284 excitation Effects 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 239000010431 corundum Substances 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(III) nitrate Inorganic materials [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 2
- 229910018057 ScCl3 Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 230000010354 integration Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000010792 warming Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 5
- 241001025261 Neoraja caerulea Species 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 3
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 3
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OQRMRSDZEJMEHR-UHFFFAOYSA-N acetic acid;scandium Chemical compound [Sc].CC(O)=O OQRMRSDZEJMEHR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 1
- 229940094800 barium oxalate Drugs 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229960001759 cerium oxalate Drugs 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KOQOJLXRPCIFKW-UHFFFAOYSA-N oxalic acid scandium Chemical compound [Sc].C(C(=O)O)(=O)O.[Sc] KOQOJLXRPCIFKW-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The present invention discloses a kind of yellow fluorescent powder and preparation method thereof and the application in field of LED illumination, belongs to luminescent material preparation and application field.Fluorescent material composition expression formula is Ba (CexSc1‑x)2O4, wherein, 0 ＜ x≤0.5.By by Ba sources, Ce sources and Sc source compounds according to mol ratio Ba:Ce:Sc=1:2x:2 2x dispensings, and mixed successively, briquetting, just burnings, grinding, briquetting, two burnings and grinding, you can obtain the yellow fluorescent powder.With reference to the diode chip for backlight unit and above-mentioned yellow fluorescent powder that launch wavelength is 430 460 nm, you can realize the preparation of white light LED luminescent device.Above-mentioned yellow fluorescent powder proposed by the invention and its preparation manufacture craft of associated light emitting device are simple, it is easy to operate, beneficial to material devices integration and Integration Design is realized, with industrialization and the potentiality produced in batches.
Description
Technical field
The invention belongs to luminescent material and its preparation field, it is related to a kind of yellow fluorescent powder and preparation method and it is lighting
Application in device.
Background technology
Compared to traditional incandescent lamp and fluorescent lighting, White-light LED illumination is as lighting source of new generation, with power consumption
The advantages of measuring fast small, long lifespan, reaction speed and small volume, it has also become current lighting field prior development direction.At present,
White light LEDs implementation method typically has following two：1st, it is combined realization by three kinds of LED of red, green and blue.Although this method can be with
The white light output of different-colour is realized, but cost is higher.2nd, using single blue light or ultraviolet leds, with reference to corresponding fluorescent material,
Realize the luminous of different-colour region.Such method not only can effectively reduce design cost, and special by adjusting fluorescent material
Property can realize different white applications demands, be the mainstay scheme of Current commercial white light LEDs.Wherein, based on single
The design of fluorescent material can more effectively avoid the colo(u)r bias that the different thermal quenching characteristics of a variety of fluorescent material are brought, and cost is lower
It is honest and clean, beneficial to realizing industrialization and production in enormous quantities.Blue-ray LED combination Ce:YAG fluorescent powder（Day is sub- chemical（Nichia）
US599892 patents）The white light LEDs output realized is to be widely recognized at present, and the white light LEDs being widely used
Implementation.However, due to Ce:YAG lacks the covering of visible light wave range red light region, the white light LEDs output colour temperature realized
It is higher, it is unfavorable for realizing that warm white LED is exported（Colour temperature<4000 K）, it is necessary to which bound fraction red fluorescence powder improves its colour temperature
With the corresponding red spectral band colour rendering index of raising（R9）.Therefore, the yellow fluorescent powder of development covering visible light red spectral band is still
White light LEDs（Especially warm white LED）Illuminate the active demand of development.
The content of the invention
For deficiencies of the prior art, the present invention provide a kind of yellow fluorescent powder and preparation method thereof and its
Application in luminescent device.
Technical scheme is as follows：
A kind of yellow fluorescent powder, chemical general formula is Ba (CexSc1-x)2O4, wherein, 0 ＜ x≤0.5, preferably 0 ＜ x≤0.05.
Further, the yellow fluorescent powder average grain diameter is 0.5~15 μm.
Further, the yellow fluorescent powder, excitation wavelength is 375~500 nm, and launch wavelength is 500~750 nm；
Excitation wavelength is preferably 430~450 nm.
A kind of preparation method of the yellow fluorescent powder, step includes：
1) according to mol ratio Ba:Ce:Sc is 1:2x:2-2x takes Ba source compounds, Ce source compounds and Sc source compounds, passes through
Alcohol wet mixing or the dry-mixed method mixing of ball milling, and be ground, obtain the powder that average grain diameter is 0.5~20 μm；
2) by step 1）The powder briquetting mixed, 0.5~20 h is then just burnt in 1000~1500 DEG C of air, is down to
After room temperature, it is ground, obtains just burning block shape powder；
3) by step 2）First burning block shape powder carry out briquetting again, then in reducing atmosphere, in 1300~1900 DEG C of progress
Two burn 1~20 h, be down to room temperature, the block powder of sintering is ground, and Ba (Ce are madexSc1-x)2O4, i.e. yellow fluorescent powder.
Further, step 1）In, the Ba source compounds, Ce source compounds and Sc source compounds purity are more than 99.9%,
Average grain diameter is at 0.5~5 μm.
Further, step 1）In, the Ba sources are BaO（Barium monoxide）、Ba(NO3)2（Barium nitrate）、BaCl2（Chlorination
Barium）、Ba(OH)2（Barium hydroxide）、BaCO3（Barium carbonate）、BaC2O4（Barium oxalate）With Ba (CH2COOH)2（Barium acetate）In extremely
Few one kind, preferably BaCO3。
Further, step 1）In, the Ce sources are CeO2（Cerium oxide）、Ce(NO3)3（Cerous nitrate）、CeCl3（Chlorination
Cerium）、Ce2(C2O4)3（Cerium oxalate）With Ce (CH2COOH)3（Cerous acetate）At least one of, preferably CeO2。
Further, step 1）In, the Sc sources are Sc2O3（Scandium oxide）、Sc(NO3)3（Scandium nitrate）、ScCl3（Chlorination
Scandium）、Sc2(C2O4)3（Oxalic acid scandium）With Sc (CH2COOH)3（Acetic acid scandium）At least one of, preferably Sc2O3。
Further, step 1）In, preferably ethanol wet mixing, incorporation time is 0.5~3 h.
Further, step 2）In, described just to burn, preferably 1200~1400 DEG C of temperature, time preferably 4~7 h.
Further, step 3）In, the reducing atmosphere is the covering of hot carbon, H2、CO、H2/N2、H2/Ar、CO/N2And CO/Ar
At least one of.
Further, step 3）In, described two burn, preferably 1400~1700 DEG C of temperature, time preferably 4~6 h.
Further, step 2）With step 3）In, the pressure of briquetting process is 30~60 MPa, and compacting shape is preferably justified
Column or square block；Briquetting size is adjusted according to the space of sintering furnace, and briquetting purpose is increase powder consistency, is suppressed close
Degree reaches 90 more than % of solid density.
Further, step 2）Described in just burn and step 3）Described in two burn, heating rate and rate of temperature fall be 2~
5 DEG C/min, carried out preferably in corundum crucible or platinum crucible.
Further, step 2）With step 3）In, preferably 0.5~15 μm of powder average grain diameter after grinding.
Present invention also offers application of the above-mentioned yellow fluorescent powder in luminescent device, it is particularly suitable for use in and is shone in white light LEDs
Application in bright.
A kind of luminescent device for including yellow fluorescent powder of the present invention, preparation method is to mix resin with yellow fluorescent powder
It is even, uniformly it is spin-coated in LED chip, dry solidification produces luminescent device.
Further, in the above method, the resin is epoxy resin or silicones, preferred index>1.4 silicon tree
Fat；
Further, in the above method, it is 5 that the yellow fluorescent powder, which accounts for resin with the percentage composition in yellow fluorescence powder mixture,
~80 wt.%.
Further, in the above method, preferred emission wavelength is 430~460 nm LED chip.
Yellow fluorescent powder of the present invention and based on luminescent device thereon, has the advantage that：
1st, Ba (Ce in the present inventionxSc1-x)2O4BaSc used in yellow fluorescent powder2O4Matrix is congruent melting compound, and fusing point is high
Up to 2100 DEG C, belong to monoclinic system C2/c space groups（Agafonov V, Kahn A, Michel D, et al. Crystal
structure of BaSc2O4; its relation with perovskite[J]. Materials research
bulletin, 1983, 18(8): 975-981）, physicochemical properties stabilization.
2、Ba(CexSc1-x)2O4Fluorescence emission wavelengths cover 475~750 nm, with high luminous efficiency, and center is sent out
Ejected wave length is in 580 nm or so；Compared to Ce:YAG（Center emission wavelength is about 550 nm）, Ba (CexSc1-x)2O4Fluorescent material can
More effectively to improve corresponding red spectral band colour rendering index（R9）, reduce colour temperature, beneficial to realize warm white LED illuminate.
3rd, Ba (Ce are prepared using solid-phase sinteringxSc1-x)2O4Yellow fluorescent powder, technique is simple, it is easy to operate；Adjust fluorescence
The concentration of powder and mixed with resin, with reference to 430~460 nm LED chip, it is possible to achieve the white-light illuminating of different-colour requirement；It is whole
Individual preparation process is with short production cycle, and production efficiency is high, beneficial to material devices integration and Integration Design is realized, with industrialization
With the potentiality of batch production.
Brief description of the drawings
Fig. 1 is the X-ray powder diffraction data of the yellow fluorescent powder of embodiment 2, and (a) is Ba (CexSc1-x)2O4X-ray
Powder diffraction data, (b) is standard BaSc2O4（ICSD：35592）Theoretical X-ray powder diffraction data；
Fig. 2 is the excitation spectrum of the yellow fluorescent powder of embodiment 2（When launch wavelength is 585 nm）And emission spectrum（Excitation wavelength is
445 nm）；
Fig. 3 is the excitation spectrum of the yellow fluorescent powder of embodiment 3（When launch wavelength is 575 nm）And emission spectrum（Excitation wavelength is
435 nm）；
Fig. 4 is the excitation spectrum of the yellow fluorescent powder of embodiment 5（When launch wavelength is 575 nm）And emission spectrum（Excitation wavelength is
435 nm）；
Fig. 5 is the white light LED part of embodiment 6, in figure：1st, resin, 2, closing line, 3, contain Ba (CexSc1-x)2O4Fluorescent material
Resin, 4, blue-light LED chip, 5, anode connection, 6, cathode connection, 7, Ba (CexSc1-x)2O4Fluorescent material absorbs blue-ray LED transmitting
Light and the sodium yellow that produces, 8, the blue light of blue-ray LED transmitting.
Embodiment
The explanation detailed, complete to technical solution of the present invention progress and description with reference to the accompanying drawings and examples.
Embodiment 1：
One kind (Ce0.003Sc0.997)2O4Yellow fluorescent powder, preparation method step is as follows：
1）With BaO, Sc2O3With Ce (NO3)3As initial feed, according to Ba:Ce:Sc mol ratio is 1:0.04:1.96 carry out
Dispensing, using dry-mixed 5 h of planetary ball mill and is ground, and obtains the powder of uniform particle sizes' distribution；
2) by step 1）The powder mixed is pressed into cylindric under 40 MPa, is put into platinum crucible, with 2~5 DEG C/min
1300 DEG C are warming up to, 5 h are burnt at the beginning of 1300 DEG C in atmosphere, room temperature is then down to 2~5 DEG C/min, is ground, is put down
The first burning block shape powder of equal 0.5~15 μm of particle diameter；
3) by step 2）The first burning block shape powder briquet under 40 MPa again, be put into platinum crucible, in CO/Ar（Body
Product is than being 5:90）Reducing atmosphere in, 1500 DEG C of two 5 h of burning is warming up to 2~5 DEG C/min, corresponding block powder is obtained, grinds
Grind the powder for 0.5~15 μm of average grain diameter, you can obtain final Ba (Ce0.003Sc0.997)2O4Yellow fluorescent powder.
Embodiment 2：
A kind of Ba (Ce0.003Sc0.997)2O4Yellow fluorescent powder, preparation method step is as follows：
1）With BaCO3、Sc2O3And CeO2As initial feed, according to Ba:Ce:Sc mol ratio is 1:0.006:1.994 carry out
Dispensing, using the h of alcoholic solution wet mixing 1, then dries and is ground in fume hood at room temperature, obtains uniform particle sizes' distribution
Powder；
2) by step 1）The powder mixed is pressed into cylindric under 40 MPa, is put into corundum crucible, with 2~5 DEG C/min
1300 DEG C are warming up to, 5 h are burnt at the beginning of 1300 DEG C in atmosphere, room temperature is then down to 2~5 DEG C/min, is ground, is put down
The first burning block shape powder of equal 0.5~15 μm of particle diameter；
3) by step 2）The first burning block shape powder briquet under 40 MPa again, be put into corundum crucible, in H2/N2（Body
Product is than being 5:95）In reducing atmosphere, 1500 DEG C of two 5 h of burning is warming up to 2~5 DEG C/min, corresponding block powder is obtained, carries out
Grinding, you can obtain final Ba (Ce0.003Sc0.997)2O4Yellow fluorescent powder.
As shown in figure 1, the X-ray powder diffraction data of this fluorescent material have good uniformity with standard diffraction card,
Illustrating the fluorescent material of sintering has and BaSc2O4Consistent crystal structure.
As shown in Fig. 2 the yellow fluorescent powder of embodiment 2, a length of 445 nm of optimum excitation wave, highest launch wavelength is 585
nm。
Embodiment 3：
A kind of Ba (Ce0.003Sc0.997)2O4Yellow fluorescent powder, preparation method step is as follows：
1）With BaCO3、Sc2O3And CeO2As initial feed, according to Ba:Ce:Sc mol ratio is 1:0.006:1.994 carry out
Dispensing, using the h of alcoholic solution wet mixing 1, then dries and is ground in fume hood at room temperature, obtains uniform particle sizes' distribution
Powder；
2) by step 1）The powder mixed briquet under 40 MPa, is put into corundum crucible, is heated up with 2~5 DEG C/min
To 1300 DEG C, 5 h are burnt at the beginning of 1300 DEG C in atmosphere, room temperature is then down to 2~5 DEG C/min, is ground, average grain is obtained
The first burning block shape powder in 0.5~15 μm of footpath；
3) by step 2）First burning block shape powder be pressed into again under 40 MPa cylindric, be put into corundum crucible, in H2/N2
（Volume ratio is 5:95）In reducing atmosphere, 1600 DEG C of two 5 h of burning is warming up to 2~5 DEG C/min, corresponding block powder is obtained,
It is ground, you can obtain final Ba (Ce0.003Sc0.997)2O4Yellow fluorescent powder.
Compared to embodiment 2（1500 DEG C of two burning）, embodiment 3（1600 DEG C of two burning）Yellow fluorescent powder（As shown in Figure 3）
Maximum excitation wavelength is changed into 435 nm；Highest launch wavelength is changed into 575 nm, and emissive porwer is doubled.This says
The bright sintering temperature that improves is conducive to improving the performance of yellow fluorescent powder.
Embodiment 4：
A kind of Ba (Ce0.02Sc0.98)2O4Yellow fluorescent powder, preparation method step is as follows：
1）With BaO, Sc2(C2O4)3With Ce (NO3)3As initial feed, according to Ba:Ce:Sc mol ratio is 1:0.04:1.96
Dispensing is carried out, using dry-mixed 5 h of planetary ball mill and is ground, the powder of uniform particle sizes' distribution is obtained；
2) by step 1）The powder mixed is pressed into square block under 40 MPa, is put into platinum crucible, with 2~5 DEG C/min
1300 DEG C are warming up to, 5 h are burnt at the beginning of 1300 DEG C in atmosphere, room temperature is then down to 2~5 DEG C/min, is ground, is put down
The first burning block shape powder of equal 0.5~15 μm of particle diameter；
3) by step 2）The first burning block shape powder briquet under 40 MPa again, be put into platinum crucible, in CO/Ar（Body
Product is than being 10:90）Reducing atmosphere in, 1600 DEG C of two 5 h of burning is warming up to 2~5 DEG C/min, corresponding block powder is obtained,
It is ground to the powder of 0.5~15 μm of average grain diameter, you can obtain final Ba (Ce0.02Sc0.98)2O4Yellow fluorescent powder.
Embodiment 5：
A kind of Ba (Ce0.02Sc0.98)2O4Yellow fluorescent powder, preparation method step is as follows：
1）With BaCO3、Sc2O3And CeO2As initial feed, according to Ba:Ce:Sc mol ratio is 1:0.04:1.96 matched somebody with somebody
Material, using the h of wet mixing in alcoholic solution 1, then dries and is ground in fume hood at room temperature, obtains uniform particle sizes' distribution
Powder；
2) by step 1）The powder mixed briquet under 40 MPa, is put into corundum crucible, is heated up with 2~5 DEG C/min
To 1300 DEG C, 5 h of sintering are burnt at the beginning of 1300 DEG C in atmosphere, room temperature is then down to 2~5 DEG C/min, is ground, is put down
The first burning block shape powder of equal 0.5~15 μm of particle diameter；
3) by step 2）First burning block shape powder under 40 MPa briquet, be put into corundum crucible, in H2/N2（Volume ratio
For 5:95）1500 DEG C of 4 h of sintering in reducing atmosphere, obtain corresponding block powder, are ground, you can obtain final Ba
(Ce0.02Sc0.98)2O4Yellow fluorescent powder.
The yellow fluorescent powder of embodiment 5, maximum excitation wavelength（435 nm）With highest launch wavelength（575 nm）.
As shown in Figure 3 and Figure 4, Ba (Ce0.003Sc0.997)2O4With Ba (Ce0.02Sc0.98)2O4Fluorescent material is excited and launched
Characteristic peak is very consistent, further illustrates the repeatability of technical solution of the present invention.In addition, along with the increase of concentration, it is sent out
The trend of reduction is presented in light efficiency, further specifies effective Ce3+Ion doping concentration range.
Embodiment 6：
A kind of luminescent device for including yellow fluorescent powder of the present invention, main working parts are Ba (Ce0.003Sc0.997)2O4Yellow is glimmering
Light powder and the blue-light LED chip that launch wavelength is 450 nm；
It is specific as follows：By silicones and yellow fluorescent powder in mass ratio 1:1 is well mixed, and is uniformly spin-coated in LED chip, dries
Solidification, i.e. white light LED part, structure are as shown in Figure 5.Without the other fluorescent material of addition in the present embodiment 6, by the use of being used as solidification
Ba(Ce0.003Sc0.997)2O4Fluorescent material and the material of outer enclosure protection.After this device switches on power, sent out using blue-ray LED
The blue light gone out（8 in Fig. 5）The yellow that blue light is sent is absorbed with fluorescent material（7 in Fig. 5）White light output can be achieved.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and modification, but these corresponding changes and change ought can be made according to the present invention by knowing those skilled in the art
Shape should all belong to the protection domain of appended claims of the invention.
Claims (10)
1. a kind of yellow fluorescent powder, it is characterised in that：Chemical general formula is Ba (CexSc1-x)2O4, wherein, 0 ＜ x≤0.5.
2. yellow fluorescent powder according to claim 1, it is characterised in that：0 ＜ x≤0.05；The yellow fluorescent powder is averaged
Particle diameter is 0.5~15 μm, and excitation wavelength is 375~500 nm, and launch wavelength is 500~750 nm.
3. yellow fluorescent powder according to claim 2, it is characterised in that：Excitation wavelength is 430~450 nm.
4. the preparation method of any one of a kind of claims 1 to 3 yellow fluorescent powder, it is characterised in that step includes：
1) according to mol ratio Ba:Ce:Sc is 1:2x:2-2x takes Ba source compounds, Ce source compounds and Sc source compounds, passes through
Alcohol wet mixing or the dry-mixed method mixing of ball milling, and be ground, obtain the powder that average grain diameter is 0.5~20 μm；
2) by step 1）The powder briquetting mixed, 0.5~20 h is then just burnt in 1000~1500 DEG C of air, is down to
After room temperature, it is ground, obtains just burning block shape powder；
3) by step 2）First burning block shape powder carry out briquetting again, then in reducing atmosphere, in 1300~1900 DEG C of progress
Two burn 1~20 h, be down to room temperature, the block powder of sintering is ground, and Ba (Ce are madexSc1-x)2O4, i.e. yellow fluorescent powder.
5. preparation method according to claim 4, it is characterised in that：Step 1）In, the Ba source compounds, Ce sources chemical combination
Thing and Sc source compounds purity are more than 99.9%, and average grain diameter is at 0.5~5 μm；The Ba sources are BaO, Ba (NO3)2、BaCl2、
Ba(OH)2、BaCO3、BaC2O4With Ba (CH2COOH)2At least one of；The Ce sources are CeO2、Ce(NO3)3、CeCl3、Ce2
(C2O4)3With Ce (CH2COOH)3At least one of；The Sc sources are Sc2O3、Sc(NO3)3、ScCl3、Sc2(C2O4)3And Sc
(CH2COOH)3At least one of；Mixed method is alcohol wet mixing, and incorporation time is 0.5~3 h；
Step 2）In, described just to burn, 1200~1400 DEG C of temperature, the h of time 4~7；
Step 3）In, the reducing atmosphere is the covering of hot carbon, H2、CO、H2/N2、H2/Ar、CO/N2At least one of with CO/Ar；
Described two burn, 1400~1700 DEG C of temperature, the h of time 4~6.
6. preparation method according to claim 5, it is characterised in that：Step 1）In, the Ba sources are BaCO3；The Ce sources
For CeO2；The Sc sources are Sc2O3。
7. preparation method according to claim 4, it is characterised in that：Step 2）With step 3）In, the pressure of briquetting process
It is 30~60 MPa, compacting is shaped as cylindric or square block；Powder average grain diameter is 0.5~15 μm after grinding；Step 2）
Described in just burn and step 3）Described in two burn, heating rate and rate of temperature fall are 2~5 DEG C/min, in corundum crucible or platinum
Carried out in golden crucible.
8. a kind of luminescent device for including any one of the claims 1 to 3 yellow fluorescent powder, it is characterised in that：Preparation method
For resin is well mixed with yellow fluorescent powder, uniformly it is spin-coated in LED chip, dry solidification produces luminescent device.
9. luminescent device according to claim 8, it is characterised in that：The resin is epoxy resin or silicones；The Huang
It is 5~80 wt.% that color fluorescent material, which accounts for resin with the percentage composition in yellow fluorescence powder mixture,；LED chip is that launch wavelength is
430~460 nm LED chip.
10. luminescent device according to claim 9, it is characterised in that：The resin is refractive index>1.4 silicones.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903896A (en) * | 2017-11-13 | 2018-04-13 | 河北紫旭节能环保技术咨询有限公司 | A kind of green emitting phosphor and preparation method thereof |
| CN109135745A (en) * | 2018-09-13 | 2019-01-04 | 济南大学 | A kind of preparation method and applications of Yellow fluorescent powder used by white light LED |
| CN110118312A (en) * | 2018-02-07 | 2019-08-13 | 深圳光峰科技股份有限公司 | Wavelength converter |
| CN110144219A (en) * | 2019-06-25 | 2019-08-20 | 长春工业大学 | A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof |
| CN111139074A (en) * | 2020-01-21 | 2020-05-12 | 济南大学 | Temperature-sensitive fluorescent powder and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1981391A (en) * | 2004-06-30 | 2007-06-13 | 三菱化学株式会社 | Light emitting device and illuminator employing it, back light for display, and display |
| CN102858914A (en) * | 2010-04-19 | 2013-01-02 | 夏普株式会社 | Red-type light emitting phosphor, method for producing same and light emitting device using red-type light emitting phosphor |
| CN103013514A (en) * | 2012-12-22 | 2013-04-03 | 广州有色金属研究院 | Green phosphor activated by cerium ions |
| CN103228825A (en) * | 2010-12-06 | 2013-07-31 | 皇家飞利浦电子股份有限公司 | Method for increasing the content of Ce<3+> in laser materials |
-
2017
- 2017-05-18 CN CN201710352345.7A patent/CN106978176B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1981391A (en) * | 2004-06-30 | 2007-06-13 | 三菱化学株式会社 | Light emitting device and illuminator employing it, back light for display, and display |
| CN102858914A (en) * | 2010-04-19 | 2013-01-02 | 夏普株式会社 | Red-type light emitting phosphor, method for producing same and light emitting device using red-type light emitting phosphor |
| CN103228825A (en) * | 2010-12-06 | 2013-07-31 | 皇家飞利浦电子股份有限公司 | Method for increasing the content of Ce<3+> in laser materials |
| CN103013514A (en) * | 2012-12-22 | 2013-04-03 | 广州有色金属研究院 | Green phosphor activated by cerium ions |
Non-Patent Citations (1)
| Title |
|---|
| YIBOCHEN等: "Low temperature quenching and high efficiency Tm3+, La3+ or Tb3+ co-doped CaSc2O4:Ce3+ phosphors for light-emitting diodes", 《JOURNAL OF LUMINESCENCE》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903896A (en) * | 2017-11-13 | 2018-04-13 | 河北紫旭节能环保技术咨询有限公司 | A kind of green emitting phosphor and preparation method thereof |
| CN110118312A (en) * | 2018-02-07 | 2019-08-13 | 深圳光峰科技股份有限公司 | Wavelength converter |
| CN109135745A (en) * | 2018-09-13 | 2019-01-04 | 济南大学 | A kind of preparation method and applications of Yellow fluorescent powder used by white light LED |
| CN109135745B (en) * | 2018-09-13 | 2021-12-14 | 济南大学 | Preparation method and application of yellow fluorescent powder for white light LED |
| CN110144219A (en) * | 2019-06-25 | 2019-08-20 | 长春工业大学 | A kind of nanoscale alkaline earth scandium oxide up-conversion luminescent material and preparation method thereof |
| CN111139074A (en) * | 2020-01-21 | 2020-05-12 | 济南大学 | Temperature-sensitive fluorescent powder and preparation method and application thereof |
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