CN108559494A - A kind of green emitting phosphor and preparation method thereof - Google Patents
A kind of green emitting phosphor and preparation method thereof Download PDFInfo
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- CN108559494A CN108559494A CN201810517493.4A CN201810517493A CN108559494A CN 108559494 A CN108559494 A CN 108559494A CN 201810517493 A CN201810517493 A CN 201810517493A CN 108559494 A CN108559494 A CN 108559494A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 22
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 21
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 18
- 239000004327 boric acid Substances 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 9
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 description 14
- 229910052593 corundum Inorganic materials 0.000 description 14
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- 229910052909 inorganic silicate Inorganic materials 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 230000005284 excitation Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 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 4
- 238000000034 method Methods 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 3
- LMEHHJBYKPTNLM-UHFFFAOYSA-H terbium(3+);tricarbonate Chemical compound [Tb+3].[Tb+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O LMEHHJBYKPTNLM-UHFFFAOYSA-H 0.000 description 3
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910003451 terbium oxide Inorganic materials 0.000 description 2
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910014779 CaAl4 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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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
- C09K11/7774—Aluminates
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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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
A kind of green emitting phosphor of present invention offer and preparation method thereof, the chemical general formula of the green emitting phosphor is MxN1‑x‑y‑zAl4O7：YCe, zTb, wherein, M is selected from by one of constituted group of Li, Na and K or several combinations, and N is selected from by one of constituted group of Ca, Mg, Sr and Ba or several combinations, 0≤x ＜ 1,0.005≤y≤0.05,0 z≤0.15 ＜；The preparation process of the green emitting phosphor includes, by chemical general formula MxN1‑x‑y‑ zAl4O7：YCe, mole metering in zTb than weighing the raw material of each component and the fluxing agent of certain mass score respectively, the raw material of above-mentioned each component and fluxing agent are fully ground and is uniformly mixed and then carries out high temperature sintering under reducing atmosphere, is cooled to room temperature, product is pulverized to obtain green emitting phosphor.Green emitting phosphor of the present invention matches well near ultraviolet chip, and energy transfer efficiency is high, and light emission luminance is high, and quantum efficiency is high, can be used for white light LEDs and other illumination fields.
Description
Technical field
The present invention relates to luminescent material technical fields, more particularly to a kind of green emitting phosphor and preparation method thereof.
Background technology
White light light emitting diode have develop the color, many merits such as brightness is high, the low, long lifespan that consumes energy, develop and receive
The concern of people.Currently, obtain the approach of white light LEDs about there are three types of, i.e. light conversion hysteria, polychromatic combination type and multiple quantum wells
Type.Realize industrialization at present is light conversion hysteria white light LEDs, and the research of light conversion material is in current luminescent material research field
Advanced subject.
There are two types of modes at present for light conversion hysteria：One, light conversion material is coated on chip, partially absorbs the indigo plant of chip emission
Light, and the yellow light of be excited generation and blue light complementation are mixed the blue light of chip and the yellow light of excitation to obtain using lens principle
To white light；In the 1990s, the breakthrough with the brightness blue light LED using InGaN materials technically, went out in 1996
Show and has mixed Ce with GaN blue-light semiconductor chips excitation generation 550nm yellow lights3+Yttrium aluminium garnet [Y3Al5O12：Ce3+(YAG：Ce3 +)] fluorescent powder, blue light and yellow light mixing obtain white light.But since the decay rates of chip and fluorescent powder are inconsistent, cause to be closed
At white light colour temperature it is higher, colour rendering index is low.Two, the chip of luminescence can be generated by being coated in several light conversion material
On, it all absorbs the transmitting of chip and is inspired red, green, blue transmitting light, white light is obtained to compound.Near ultraviolet excitation type is white
The color of light LED is only determined by fluorescent powder itself, therefore its colour rendering index is high, and colour temperature is low, and stability is good, however Vehicles Collected from Market
On green emitting phosphor luminous efficiency it is relatively low, such as commercial (Ba, Sr)2SiO4：Eu2+Green emitting phosphor (the patent No.
CN103194220A quantum efficiency), which is 70-80%, will reach same lighting requirements, and it is glimmering just to must be added to more greens
Light powder, increases production cost.
Therefore, it finds one kind to match near ultraviolet chip well, energy transfer efficiency is high, and luminous efficiency is high, and brightness is high
Green emitting phosphor reduces Near ultraviolet excitation type white light LEDs production cost, becomes one of those skilled in the art's urgent need to resolve
Problem.
Invention content
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of green emitting phosphor and its preparations
Method, low for solving green emitting phosphor luminous efficiency in the prior art, brightness is low, and leads to Near ultraviolet excitation type white light LEDs
The high problem of production cost.
In order to achieve the above objects and other related objects, the present invention provides a kind of green emitting phosphor, the green emitting phosphor
Chemical general formula it is as described below：
MxN1-x-y-zAl4O7：YCe, zTb
Wherein, M is selected from by one of constituted group of Li, Na and K or several combinations, plays charge compensation
Effect；N is selected from by one of constituted group of Ca, Mg, Sr and Ba or several combinations；0≤x ＜ 1,0.005≤y≤
0.05,0 z≤0.15 ＜.
A kind of preferred embodiment of the green emitting phosphor as the present invention, the x meet the following conditions：X=0.
A kind of preferred embodiment of the green emitting phosphor as the present invention, the N include Ca.
A kind of preferred embodiment of the green emitting phosphor as the present invention, the y meet the following conditions：Y=0.04.
A kind of preferred embodiment of the green emitting phosphor as the present invention, the z meet the following conditions：0.02≤z≤
0.06。
A kind of preferred embodiment of the green emitting phosphor as the present invention, the z meet the following conditions：Z=0.04.
The present invention also provides a kind of preparation method of green emitting phosphor, the preparation method uses high temperature in the prior art
Solid-phase synthesis includes the following steps：
S10, chemical general formula M is pressedxN1-x-y-zAl4O7：The raw material mole measured than weighing each component respectively in yCe, zTb
And the fluxing agent of certain mass score, fluxing agent be in order to promote green emitting phosphor at phase；
S20, the step S10 raw materials weighed and the fluxing agent are fully ground it is uniformly mixed；
S30, it will be fully ground the uniformly mixed raw material in step S20 carries out high temperature sintering in a reducing atmosphere, with
Postcooling is to room temperature；
S40, the product of the high temperature sintering in step S30 is pulverized.
The improvement of the preparation method of the green emitting phosphor as the present invention, the chemical general formula MxN1-x-y-zAl4O7：
In yCe, zTb, the raw material of the M is selected from by the carbon of Li, one of constituted groups of each K of Na or in which several combinations
Hydrochlorate or bicarbonate；The raw material of the N is selected from by one of constituted group of Ca, Mg, Sr and Ba or in which several
Combination oxide or heat treatment after produce the oxide carbonization salt, nitrate or oxalates；The raw material of the aluminium is
Al2O3；The raw material of the cerium is selected from by CeO2, one of cerous nitrate and the constituted group of cerous carbonate；The raw material of the terbium
Selected from by terbium oxide, one of terbium nitrate and the constituted group of terbium carbonate.
The improvement of the preparation method of the green emitting phosphor as the present invention, the reducing atmosphere is that volume ratio is 10%
H2And 90%N2Mixed gas.
The improvement of the preparation method of the green emitting phosphor as the present invention, the temperature of the high temperature sintering is 1400~
1500 DEG C, the time is 3~6h.
The improvement of the preparation method of the green emitting phosphor as the present invention, the fluxing agent are selected from by boric acid, fluorine
Change one of ammonium and the constituted group of boron oxide or several combinations.
The amount of the improvement of the preparation method of the green emitting phosphor as the present invention, the boric acid is green emitting phosphor base
The chemical formula of the 8% of matter mole, the green emitting phosphor matrix is NAl4O7。
It should be noted that green emitting phosphor matrix refers to the green emitting phosphor in no doping M, Ce, when Tb elements
Matrix.
The present invention also provides a kind of white light LEDs of encapsulation, the white light LEDs of the encapsulation by the present invention green emitting phosphor,
Commercial red fluorescence powder CaAlSiN3：Eu2+With commercial blue colour fluorescent powder BaMgAl10O17：Eu2+It encapsulates.
As described above, the green emitting phosphor and preparation method thereof of the present invention, has the advantages that：The present invention's is described
Green emitting phosphor is that Ce is mixed in matrix3+And Tb3+Ion utilizes Ce3+Energy is efficiently passed into Tb as sensitizer3+
The green light for inspiring high brightness, reduces production cost；This green emitting phosphor luminous efficiency is high, and quantum efficiency reaches
92.55%, light emission luminance is commercial powder (Ba, Sr)2SiO4：Eu2+2.45 times；And matched near ultraviolet chip well, it can
For white light LEDs and other illumination fields.
Description of the drawings
Fig. 1 is shown as the preparation method flow diagram of the green emitting phosphor of the present invention.
Fig. 2 is respectively indicated as the green emitting phosphor (a) in the embodiment of the present invention 1 and international crystal diffraction standard card JCPDS：
The XRD spectrum of 23-1037 (b).
Fig. 3 is shown as the green emitting phosphor in embodiment 1 and commercial powder (Ba, Sr)2SiO4：Eu2+Excitation-emission (PL)
Spectrum.The green emitting phosphor shown in solid in the embodiment of the present invention 1 under the excitation of 350nm, transmitting 360~
Within the scope of 700nm, wherein 375~475nm belongs to Ce3+5d-4f transition, four groups of spikes of 475~650nm are respectively belonging to
Tb3+'s5D4→7F6、5D4→7F5、5D4→7F4、5D4→7F3Transition, emission peak can be used as white light LEDs green in 542nm
Fluorescent powder；Dotted line show commercial powder (Ba, Sr)2SiO4：Eu2+It is surveyed with the green emitting phosphor in the embodiment of the present invention 1
Emission spectrum when strip part is identical；
Fig. 4 is shown as the green emitting phosphor in embodiment 1 and primary standard substance BaSO4Emission spectrum and scattering spectrum.It can root
According to formula
To calculate the quantum efficiency of sample.Wherein, in formula, QY indicates quantum efficiency, EsampleIndicate the emission spectra of sample
Integral area, EblankIndicate object of reference (BaSO4) emission spectra integral area, SsampleIndicate the product of the scattering spectra of sample
Facet is accumulated, SblankIndicate the scattering spectra integral area of object of reference.
Fig. 5 is shown as the green emitting phosphor in the embodiment of the present invention 1 and commercial rouge and powder CaAlSiN3：Eu2+And blue powder
BaMgAl10O17：Eu2+The launching light spectrogram of the LED of encapsulation.
Component label instructions
S10~S40 steps
Specific implementation mode
Illustrate that embodiments of the present invention, those skilled in the art can be by this specification below by way of specific specific example
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
It please refers to Fig.1.It should be noted that the diagram provided in the present embodiment only illustrates the present invention's in a schematic way
Basic conception, component count, shape when only display is with related component in the present invention rather than according to actual implementation in schema then
And size is drawn, when actual implementation kenel, quantity and the ratio of each component can be a kind of random change, and its assembly layout
Kenel may also be increasingly complex.
As shown in Figure 1, the preparation method of the green emitting phosphor of the present invention, using high temperature process heat in the prior art
Method includes the following steps：
Step S10 is executed, by chemical general formula N1-y-zAl4O7：Mole metering in yCe, zTb than weighing each component respectively
The fluxing agent of raw material and certain mass score, fluxing agent be in order to promote green emitting phosphor at phase.
It should be noted that the chemical general formula N1-y-zAl4O7：In yCe, zTb, the raw material of the N be selected from by Ca,
The oxidation is produced after the oxide or heat treatment of one of constituted group of Mg, Sr and Ba or in which several combinations
Carbonization salt, nitrate or the oxalates of object；The raw material of the aluminium is Al2O3；The raw material of the cerium is selected from by CeO2, cerous nitrate
One of with the constituted group of cerous carbonate；The raw material of the terbium is selected from and is made of terbium oxide, terbium nitrate and terbium carbonate
One of group.
Specifically, in following examples, the N uses Ca.
Specifically, in following examples, the raw material of the Ca uses calcium carbonate, in actual preparation process, base
In experiment condition or other consider, can also use the raw material of calcium oxide, calcium nitrate or calcium oxalate as Ca, not with reality hereafter
Example is applied to be limited；The raw material of the cerium uses CeO2, in actual preparation process, based on experiment condition or other consider, it is described
The raw material of cerium can also use cerous nitrate or cerous carbonate, be not limited with following Examples；The raw material of the terbium uses Tb4O7,
In actual preparation process, based on experiment condition or other consider, the terbium nitrate or terbium carbonate that can also select, not with hereafter
Embodiment is limited.
It should be noted that the fluxing agent can be used boric acid, ammonium fluoride, one kind of the common fluxing agent such as boron oxide or
Several combination of person.
In following examples, using boric acid as fluxing agent, the amount of the boric acid is rubbing for green emitting phosphor matrix
The chemical formula of the 8% of that amount, the green emitting phosphor matrix is NAl4O7, in actual preparation process, other can also be selected
It is suitble to the cosolvent of the system of the present invention.
As shown in Figure 1, executing step S20, the step S10 raw materials weighed and the fluxing agent are fully ground mixing
Uniformly.
Specifically, in following examples, the step S10 raw materials weighed and the fluxing agent are added in mortar
Enter absolute ethyl alcohol be fully ground it is uniformly mixed；It should be noted that can also ball-milling method etc. be used, other can realize above-mentioned purpose
The prior art is not limited to this embodiment.
As shown in Figure 1, executing step S30, the uniformly mixed raw material will be fully ground in step S20 in reducing atmosphere
Middle carry out high temperature sintering, is then cooled to room temperature.
Specifically, in following examples, volume fraction 10%H can be used in the reducing atmosphere2And 90%N2It is constituted
Mixed gas.
Specifically, the temperature of the high temperature sintering is 1400~1500 DEG C, and the time is 3~6h, in following examples,
Sintering temperature uses 1450 DEG C, and sintering time uses 4h.
As shown in Figure 1, executing step S40, the product of the high temperature sintering in step S30 being pulverized, it is glimmering to obtain green
Light powder.
It should be noted that Ce3+And Tb3+Mix NAl4O7Lattice substitute N2+When ion, the shape due to charge mismatch
At there is electronegative N2+Ionic vacancies defect, the centre of luminescence can be to electronegative N2+Ionic vacancies defect transmits energy, to right
Shining, it is unfavorable to generate.It is N to further improve chemical general formula1-y-zAl4O7：YCe, zTb (0.005≤y≤0.05,0 ＜ z
≤ 0.15) luminous intensity and quantum efficiency of green emitting phosphor can introduce element charge compensator M, reduce electronegative
N2+Ionic vacancies defects count, it is M to form chemical general formulaxN1-x-y-zAl4O7：YCe, zTb (0≤x ＜ 1,0.005≤y≤0.05,
0 z≤0.15 ＜) green emitting phosphor, the raw material of the M is selected from by Li, one of constituted groups of each K of Na or in which
The carbonate or bicarbonate of several combinations；The member that the ionic radius of the N selection ionic radius and the M are not much different
Element, such as when N uses Ca, then M uses Na, this is because Na+Ionic radius and Ca2+Ionic radius relatively, cause
Distortion of lattice smaller.
The test method in relation to data is as follows in the embodiment of the present invention：
X-ray diffraction (XRD) test is the D2PHASER desktop type X-rays produced in German Brooker company (Bruker)
It is carried out on diffractometer.Use Cu target K alpha rays (K α：).Operating voltage 30kV, electric current 10mA.It is adopted in test
Mode is step-scan, and step-length is 0.02 °, and scanning range is 5 °~80 °.
The FLS-980 Fluorescence Spectrometer produced using Edinburgh, Britain (Edinburgh) company, test are swashed near ultraviolet band
Give the characteristics of luminescence and quantum efficiency of sample.
Embodiment 1
Compare Ca according to a mole metering：Al：Ce：Tb：Boric acid=0.92：4：0.04：0.04：0.08, CaCO is weighed respectively3,
Al2O3, CeO2, Tb4O7Raw material and boric acid (fluxing agent)；The raw material and the fluxing agent weighed is fully ground in mortar
It is uniformly mixed；It is packed into corundum crucible, in volume fraction 10%H2And 90%N2Reducing atmosphere under carry out high temperature sintering, sintering temperature
Degree is 1450 DEG C, and sintering time 4h is ground after being then cooled to room temperature, obtains a kind of green emitting phosphor of the present invention,
Chemical formula is Ca0.92Al4O7：0.04Ce3+, 0.04Tb3+, wherein x=0, y=0.04, z=0.04.
Fig. 2 is respectively indicated as the green emitting phosphor (a) of the present embodiment and international crystal diffraction standard card JCPDS：23-1037
(b) XRD spectrum, it can be seen that the green emitting phosphor of the present embodiment has monocline cube CaAl4O7Structure.
Fig. 3 is shown as the green emitting phosphor of the present embodiment and commercial powder (Ba, Sr)2SiO4：Eu2+Excitation-emission (PL) light
Spectrum.As seen from the figure, the light emission luminance of the green emitting phosphor is commercial powder (Ba, Sr)2SiO4：Eu2+2.45 times.
Fig. 4 is shown as the green emitting phosphor and primary standard substance BaSO of embodiment4Emission spectrum and scattering spectrum.It can be counted by figure
The quantum efficiency for calculating the green emitting phosphor is 92.55%.
By the green emitting phosphor of the present embodiment, commercial red fluorescence powder CaAlSiN3：Eu2+It is glimmering with commercial blue
Light powder BaMgAl10O17：Eu2+Encapsulation forms white light LEDs, and launching light spectrogram is as shown in figure 5, it can be seen that its chromaticity coordinates is
(0.3461,0.3188), the chromaticity coordinates (0.33,0.33) of very close standard white light；Colour temperature is 4706K, belongs to warm white.
Embodiment 2
Compare Ca according to a mole metering：Al：Ce：Tb：Boric acid=0.958：4：0.04：0.002：0.08, it weighs respectively
CaCO3, Al2O3, CeO2, Tb4O7Raw material and boric acid (fluxing agent)；The raw material and the fluxing agent weighed fills in mortar
Divide ground and mixed uniform；It is packed into corundum crucible, in volume fraction 10%H2And 90%N2Reducing atmosphere under carry out high temperature sintering,
Sintering temperature is 1450 DEG C, and sintering time 4h is ground after being then cooled to room temperature, and a kind of green for obtaining the present invention is glimmering
Light powder, chemical formula are Ca0.958Al4O7：0.04Ce3+, 0.002Tb3+, wherein x=0, y=0.04, z=0.002.
The luminosity of the green emitting phosphor is identical as the green emitting phosphor implemented in 1, quantum efficiency and sends out brightness
It is low compared to the green emitting phosphor in embodiment 1.
Embodiment 3
Compare Ca according to a mole metering：Al：Ce：Tb：Boric acid=0.955：4：0.04：0.005：0.08, it weighs respectively
CaCO3, Al2O3, CeO2, Tb4O7Raw material and boric acid (fluxing agent)；The raw material and the fluxing agent weighed fills in mortar
Divide ground and mixed uniform；It is packed into corundum crucible, in volume fraction 10%H2And 90%N2Reducing atmosphere under carry out high temperature sintering,
Sintering temperature is 1450 DEG C, and sintering time 4h is ground after being then cooled to room temperature, and a kind of green for obtaining the present invention is glimmering
Light powder, chemical formula are Ca0.955Al4O7：0.04Ce3+, 0.002Tb3+, wherein x=0, y=0.04, z=0.005.
The luminosity of the green emitting phosphor is identical as the green emitting phosphor implemented in 1, quantum efficiency and sends out brightness
It is low compared to the green emitting phosphor in embodiment 1.
Embodiment 4
Compare Ca according to a mole metering：Al：Ce：Tb：Boric acid=0.95：4：0.04：0.01：0.08, CaCO is weighed respectively3,
Al2O3, CeO2, Tb4O7Raw material and boric acid (fluxing agent)；The raw material and the fluxing agent weighed is fully ground in mortar
It is uniformly mixed；It is packed into corundum crucible, in volume fraction 10%H2And 90%N2Reducing atmosphere under carry out high temperature sintering, sintering temperature
Degree is 1450 DEG C, and sintering time 4h is ground after being then cooled to room temperature, obtains a kind of green emitting phosphor of the present invention,
Chemical formula is Ca0.95Al4O7：0.04Ce3+, 0.01Tb3+, wherein x=0, y=0.04, z=0.01.
The luminosity of the green emitting phosphor is identical as the green emitting phosphor implemented in 1, quantum efficiency and sends out brightness
It is low compared to the green emitting phosphor in embodiment 1.
Embodiment 5
Compare Ca according to a mole metering：Al：Ce：Tb：Boric acid=0.94：4：0.04：0.02：0.08, CaCO is weighed respectively3,
Al2O3, CeO2, Tb4O7Raw material and boric acid (fluxing agent)；The raw material and the fluxing agent weighed is fully ground in mortar
It is uniformly mixed；It is packed into corundum crucible, in volume fraction 10%H2And 90%N2Reducing atmosphere under carry out high temperature sintering, sintering temperature
Degree is 1450 DEG C, and sintering time 4h is ground after being then cooled to room temperature, obtains a kind of green emitting phosphor of the present invention,
Chemical formula is Ca0.94Al4O7：0.04Ce3+, 0.02Tb3+, wherein x=0, y=0.04, z=0.02.
The luminosity of the green emitting phosphor is identical as the green emitting phosphor implemented in 1, quantum efficiency and sends out brightness
It is low compared to the green emitting phosphor in embodiment 1.
Embodiment 6
Compare Ca according to a mole metering：Al：Ce：Tb：Boric acid=0.9：4：0.04：0.06：0.08, CaCO is weighed respectively3,
Al2O3, CeO2, Tb4O7Raw material and boric acid (fluxing agent)；The raw material and the fluxing agent weighed is fully ground in mortar
It is uniformly mixed；It is packed into corundum crucible, in volume fraction 10%H2And 90%N2Reducing atmosphere under carry out high temperature sintering, sintering temperature
Degree is 1450 DEG C, and sintering time 4h is ground after being then cooled to room temperature, obtains a kind of green emitting phosphor of the present invention,
Chemical formula is Ca0.9Al4O7：0.04Ce3+, 0.06Tb3+, wherein x=0, y=0.04, z=0.06.
The luminosity of the green emitting phosphor is identical as the green emitting phosphor implemented in 1, quantum efficiency and sends out brightness
It is low compared to the green emitting phosphor in embodiment 1.
In conclusion the green emitting phosphor of the present invention is to mix Ce in its matrix3+And Tb3+Ion utilizes Ce3+
Energy is efficiently passed into Tb as sensitizer3+, the green light of high brightness is inspired, production cost is reduced；This green is glimmering
Light powder luminous efficiency is high, and quantum efficiency reaches 92.55%, and light emission luminance is commercial powder (Ba, Sr)2SiO4：Eu2+2.45 times；
And matched well near ultraviolet chip, it can be used for white light LEDs and other illumination fields.So the present invention effectively overcomes now
There is the various shortcoming in technology and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of green emitting phosphor, which is characterized in that the chemical general formula of the green emitting phosphor is as described below：
MxN1-x-y-zAl4O7：YCe, zTb
Wherein,
M is selected from by one of constituted group of Li, Na and K or several combinations；
N is selected from by one of constituted group of Ca, Mg, Sr and Ba or several combinations；
0≤x ＜ 1,0.005≤y≤0.05,0 z≤0.15 ＜.
2. a kind of green emitting phosphor according to claim 1, which is characterized in that the x meets the following conditions：X=0.
3. a kind of green emitting phosphor according to claim 2, which is characterized in that the N includes Ca.
4. a kind of green emitting phosphor according to claim 3, which is characterized in that the y meets the following conditions：Y=0.04.
5. a kind of green emitting phosphor according to claim 4, which is characterized in that the z meets the following conditions：0.02≤z
≤0.06。
6. green emitting phosphor according to claim 5, which is characterized in that the z meets the following conditions：Z=0.04.
7. a kind of a kind of preparation method of green emitting phosphor as claimed in any one of claims 1 to 6, which is characterized in that described
Preparation method includes the following steps：
S10, chemical general formula M is pressedxN1-x-y-zAl4O7：The raw material and one mole measured than weighing each component respectively in yCe, zTb
Determine the fluxing agent of mass fraction；
S20, the raw material of the step S10 each components weighed and the fluxing agent are fully ground it is uniformly mixed；
S30, it will be fully ground the uniformly mixed raw material in step S20 carries out high temperature sintering in a reducing atmosphere, it is then cold
But to room temperature；
S40, the product of the high temperature sintering in step S30 is pulverized.
8. the preparation method of green emitting phosphor according to claim 7, which is characterized in that the temperature of the high temperature sintering is
1400~1500 DEG C, the time is 3~6.
9. the preparation method of green emitting phosphor according to claim 7, which is characterized in that the fluxing agent is selected from by boron
Acid, one of ammonium fluoride and the constituted group of boron oxide or several combinations.
10. the preparation method of green emitting phosphor according to claim 9, which is characterized in that the amount of the boric acid is green
The chemical formula of the 8% of fluorescent powder matrix mole, the green emitting phosphor matrix is NAl4O7。
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Citations (2)
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| CN102719242A (en) * | 2012-05-29 | 2012-10-10 | 温州大学 | Fluoride-containing Mn<4+>-doped red-light material and preparation method thereof |
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| CN102719242A (en) * | 2012-05-29 | 2012-10-10 | 温州大学 | Fluoride-containing Mn<4+>-doped red-light material and preparation method thereof |
| CN106978181A (en) * | 2017-05-14 | 2017-07-25 | 复旦大学 | The orthogonal fluorescence-encoded anti-fake material of long afterglow is changed in a kind of near infrared light charging |
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