CN106635014A - Garnet-structure single-matrix white-light fluorescent powder and preparation method and application thereof - Google Patents
Garnet-structure single-matrix white-light fluorescent powder and preparation method and application thereof Download PDFInfo
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- CN106635014A CN106635014A CN201611095388.3A CN201611095388A CN106635014A CN 106635014 A CN106635014 A CN 106635014A CN 201611095388 A CN201611095388 A CN 201611095388A CN 106635014 A CN106635014 A CN 106635014A
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- 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
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7793—Germanates
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Abstract
The invention discloses garnet-structure single-matrix white-light fluorescent powder and a preparation method and application thereof. A chemical formula of the fluorescent powder is Mg1-a-x-zAaY2-b-yBbAl4-cCcSi1-dDdO12:xEu<3+>, yCe<3+>, zMn<2+>, wherein A refers to combination of one or two of Sr and Ca in an arbitrary proportion, B refers to combination of more than one or two of Gd, La and Lu in an arbitrary proportion, C refers to Ga, D refers to Ge, and x, y, z, a, b, c and d refers to respective mole fractions. The fluorescent powder is capable of emitting three emission peaks of blue light, yellow orange light and red light under ultraviolet excitation, white-light emission is realized in a single matrix and covers a whole visible region, and high color rendering is realized. The fluorescent powder belongs to a garnet-structure silicate system and is high in heat stability. The fluorescent powder is synthesized according to a traditional high-temperature solid reaction method, and simplicity and easiness in acquisition of raw materials, simplicity and convenience in preparation process and easiness in batch production are realized.
Description
Technical field
The invention belongs to luminescent material technical field, and in particular to be applied to the fluorescent material of semiconductor lighting, especially relate to
And a kind of can effectively being excited by UV LED chip and launch garnet structure fluorescent material of white light and its preparation method and application.
Background technology
Generally, preparing the single-substrate white fluorescent powder of ultraviolet excitation needs complicated design.Most popular method is simultaneously
Various light emitting ionics adulterate to same matrix, such as Eu3+/Tm3+/Tb3+And Ce3+/Tb3+/Mn2+Deng.Its key problem is to select
Suitable luminescent center ion, and the fluorescent material matrix of suitable these ion dopings is selected or designs, to reach a kind of fluorescence
Simultaneously transmitting can be mixed into the bluish-green red multicolor luminous of white light in powder.From for the species of light emitting ionic, because Ce3+、Eu2+
4f-5d transition be parity allow, they are doped in matrix generally can produce strong broadband emission.So, they are
Very important rare earth luminous ion, is generally used as activator ion and sensitizer ion in fluorescent material.Importantly,
Can pass through to select, the matrix composition of design fluorescent material adjusting coordination environment, allow their launch wavelength from ultraviolet red
Move on to gold-tinted, or even red light region.Additionally, Eu2+And Ce3+Generally there is Eu in the fluorescent material being co-doped with2+、Ce3+Between energy pass
Pass, the photochromic of fluorescent material can be adjusted by adjusting their relative amount.The conventional activator ion of another kind is Mn2+,
It generally produces the emission spectrum of longer wavelength.Due to Mn2+Be emitted as d-d forbidden transitions, so its emissive porwer is weaker.
However, by introducing sensitizer Eu in specific matrix2+Or Ce3+, when from Eu2+Or Ce3+To Mn2+Energy transmission can send out
When raw, Mn2+Transmitting have enhancing.
Recently, we report blue light activated yellow fluorescent powder MgY2Al4SiO12:Ce3+, its launch wavelength is 565
Nm, 23 nm than commercial fluorescence powder YAG red shifts, can be packaged into white light LEDs with blue chip.But its red light portion remains unchanged
Lack, colour rendering index is not high.Find in this matrix, be adapted to respectively Eu due to possessing in our further research2+、
Ce3+And Mn2+The case of doping, in particular, provides suitable crystal field strength, Eu2+、Ce3+And Mn2+Send out respectively in the matrix
Penetrate blue light, gold-tinted and ruddiness.Accordingly, we are with MgY2Al4SiO12For matrix, by Eu2+、Ce3+And Mn2+It is co-doped with realizing single base
Matter white emitting fluorescent powder.It is possible to further pass through to adjust Eu2+、Ce3+And Mn2+Doping content, and the ion of each case
Adulterate to realize luminous intensity, the adjustability of chromaticity coordinates of fluorescent material.
The content of the invention
Problem present in encapsulation technology for existing blue chip and yellow fluorescent powder, it is an object of the invention to carry
For a kind of new single matrix, the simple white light LEDs white emitting fluorescent powder of manufacture craft and its preparation method and application.
The technical solution used in the present invention is：
Described a kind of garnet structure single-substrate white fluorescent powder, it is characterised in that the chemical expression of the fluorescent material is：
Mg1-a-x-zAaY2-b-yBbAl4-cCcSi1-dDdO12:xEu3+,yCe3+,zMn2+
In formula：A is the combination of one or two arbitrary proportions in Sr, Ca, and B is one or more in Gd, La, Lu
The combination of arbitrary proportion；C is Ga；D is Ge；X, y, z, a, b, c, d be respective molar fraction, their span
Respectively： 0≤a≤0.2；0≤b≤0.5；0≤c≤4；0≤d≤0.3；0.005≤x≤0.10；0.005≤y≤0.12；
0.005≤z≤0.15。
A kind of described garnet structure single-substrate white fluorescent powder, it is characterised in that 0.01≤x≤0.10；0.03≤y
≤0.09；0.03≤z≤0.15.
Described a kind of garnet structure single-substrate white fluorescent powder, it is characterised in that A is Ca, B is La.
The present invention can pass through the performance of the adjustable fluorescent material of composition and content for changing A, B, C, D, wherein a, b, c and d
Can be each 0, that is, the element A that undopes, B element, C element or D elements, it is also possible to while be 0, when a, b, c and d are simultaneously 0
When, that is, represent that fluorescent material tetra- kinds of elements of A, B, C and D undope.
A kind of described garnet structure single-substrate white fluorescent powder, it is characterised in that Mg1-x-zY2-yAl4SiO12:xEu3+,
yCe3+,zMn2+。
The preparation method of described garnet structure single-substrate white fluorescent powder, comprises the following steps：
1）By described chemical expression Mg1-a-x-zAaY2-b-yBbAl4-cCcSi1-dDdO12:xEu3+,yCe3+,zMn2+In each unit
The compound of element is raw material, and by the molar ratio of each element in the chemical expression each raw material of respective quality is weighed respectively,
Each raw material solid powder mull is mixed into obtain presoma；
2）By step 1）The presoma for obtaining is placed in reducing atmosphere, is warming up to 900 DEG C～1500 DEG C roasting temperatures 1 ~ 5
It is secondary, obtain final product of roasting；Every time roasting time is 5 ~ 24 hours, is cooled to room temperature between every double roasting and is ground place
Reason, last time roasting carries out under reducing atmosphere, the reducing atmosphere be the nitrogen mixture containing 5-10v% hydrogen or
Nitrogen mixture containing 5-10v% carbon monoxide；
3）By step 2) final product of roasting Jing is broken, levigate, grain size grading, and scrubbed removal of impurities, drying be obtained described in
Garnet structure single-substrate white fluorescent powder.
The preparation method of described garnet structure single-substrate white fluorescent powder, it is characterised in that step 2）Presoma put
Roasting 1 ~ 2 time in reducing atmosphere.
The preparation method of described garnet structure single-substrate white fluorescent powder, it is characterised in that step 2）It is warming up to 900
DEG C～1500 DEG C of heating rate is 5 DEG C/min～20 DEG C/min.
The preparation method of described garnet structure single-substrate white fluorescent powder, it is characterised in that step 2）Middle grinding is in agate
Carry out in Nao mortars or ball mill.
The preparation method of described garnet structure single-substrate white fluorescent powder, it is characterised in that step 3）In final roasting
Product is adopted after hand-crushed makes the particle size of sintered body levigate with ball milling method again, Jing sedimentation, sieve method or air-flow method
Classification, it is 3 ~ 10 microns of pressed powder to take granularity, is washed 1-4 time with water or methyl alcohol, filters to isolate solid phase, in 110 DEG C ~
130 DEG C of drying 2-6 h.
The raw material of the fluorescent material is the compound for containing each element in chemical expression respectively, can be according to chemical expression
In the various elements that contain choose the compound containing the element as raw material.Specifically, the raw material of the fluorescent material includes each
The compound of self-contained Mg, Y, Al, Si, Eu, Ce, Mn, in fluorescent material adulterate A, B, C or D when, then raw material also include each self-contained A, B,
The compound of C or D；More specifically, the compound containing Mg, Ca, Sr, Eu, Mn be each self-corresponding oxide, carbonate,
Nitride, hydroxide or nitrate；Compound containing Y, Gd, La, Lu or Ce is each self-corresponding oxide, nitride, carbon
Hydrochlorate, hydroxide or nitrate；Compound containing Al, Si is corresponding oxide or nitride.
The single-substrate white fluorescent powder that the present invention is provided emits white light under ultraviolet excitation, is white emitting fluorescent powder, Ke Yiying
In white light LEDs, the method for the application is that single-substrate white fluorescent powder is encapsulated with UV LED chip, for preparing white light
LED。
The single-substrate white fluorescent powder that the present invention is provided emits white light under ultraviolet excitation, is white emitting fluorescent powder, Ke Yiying
In white light LEDs, the method for the application is that single-substrate white fluorescent powder is encapsulated with UV LED chip, for preparing white light
LED。
Compared with prior art, beneficial effects of the present invention are as follows：
1）LED white emitting fluorescent powders of the present invention, during in LED light source devices, can in the case of by ultraviolet excitation,
Can launch blue light, three emission peaks of yellow orange light and ruddiness in visible waveband, white light emission is realized in single-matrix.And send out
Penetrate peak-to-peak width wider, almost cover whole visible region, colour rendering is high, due to obtaining high quality white light a kind of fluorescence is only used
Powder, can greatly simplify technological process, with good industrialization prospect and application prospect；
2）Fluorescent material belongs to the silicate systems of garnet structure in the present invention, and heat endurance is good.The fluorescent material is by traditional
High-temperature solid phase reaction method synthesizes, and raw material is simple and easy to get, and preparation technology is easy, it is easy to produce in batches.
Description of the drawings
Fig. 1 three mixes Eu obtained in being the embodiment of the present invention 13+,Ce3+,Mn2+Aluminosilicate fluorescent powder excitation spectrum and
Launching light spectrogram, left-most curve is exciting light spectrogram in figure, and the right curve is launching light spectrogram；
Fig. 2 three mixes Eu obtained in being the embodiment of the present invention 13+,Ce3+,Mn2+Aluminosilicate fluorescent powder X-ray diffraction spectrogram.
Specific embodiment
Below the solution of the present invention is described further with specific embodiment, but protection scope of the present invention is not limited to
This.
Embodiment 1：Mg0.96Y1.94Al4SiO12:0.01Eu3+,0.06Ce3+,0.03Mn2+The preparation of fluorescent material,
Its preparation method is as follows：
0.1935 gram of magnesia is weighed respectively（MgO）, 1.0952 grams of yittrium oxide（Y2O3）, 1.0196 grams of aluminum oxide（Al2O3）、
0.3004 gram of silica（SiO2）, 0.0088 gram of urania（Eu2O3）, 0.0516 gram of cerium oxide（CeO2）, 0.0172 gram of manganese carbonate
（MnCO3）Above material purity is more than 99%.Above-mentioned raw materials mixture is fully ground in agate mortar, raw material is mixed
Close uniform.Resulting presoma is positioned in corundum crucible, under the reducing atmosphere that activated carbon is provided, in integrated atmosphere
With 10 DEG C of min in stove-1Speed be warming up to 900 DEG C, constant temperature 6h is subsequently cooled to room temperature.By the presoma after calcining again
Grinding, in activated carbon and H2/N2（5%/95%）During integrated atmosphere furnace is put under the reducing atmosphere of offer, with 10 DEG C of min-1's
Speed is warming up to 1300 DEG C, and then constant temperature 8h cools to room temperature with the furnace.Taking-up is pulverized, that is, obtain required fluorescent material sample.
Three mix Eu obtained in the present embodiment3+、Ce3+、Mn2+White emitting fluorescent powder excitation spectrum and emission spectrum spectrogram such as
Shown in accompanying drawing 1, wherein left-most curve is exciting light spectrogram, and the right curve is launching light spectrogram.It can be seen that the fluorescence
Under 340 nm burst of ultraviolel, fluorescent material produces three blue lights, three emission peaks of yellow orange light and ruddiness to powder, and they are attributed to respectively
Eu at 450 nm2+5d → 4f transition, Ce at 565 nm3+5d → 4f transition and 620 nm at Mn2+'s4T1(4G)→6A1(6S)
Transition.From 380 nm to 750, the emission spectrum of nm almost covers whole visible region, can obtain the white light of high color rendering index (CRI).
Measure its chromaticity coordinates（x=0.315,y=0.344）.The fluorescent material can be suitable by the ultraviolet excitation of the nm from 260 nm to 400
The new phosphorses of the white light LEDs application excited together in UV LED chip.Fig. 2 is MgY obtained in embodiment 11.94Al3Si2O12:
0.01Eu3+、0.06Ce3+、0.03Mn2+The XRD of fluorescent material, the standard card of Fig. 2 and garnet structure is compared, and can be seen
It is garnet structure to go out obtained fluorescent material.
Embodiment 2：Mg0.72Ca0.2Y1.94Al4SiO12:0.02Eu2+,0.06Ce3+,0.06Mn2+The preparation of fluorescent material
Preparation method is as follows：
0.1451 gram of magnesia is weighed respectively（MgO）, 0.1001 gram of calcium carbonate（CaCO3）, 1.0952 grams of yittrium oxide（Y2O3）、
1.0196 gram aluminum oxide（Al2O3）, 0.3004 gram of silica（SiO2）, 0.0176 gram of europium oxide（Eu2O3）, 0.0516 gram of cerium oxide
And 0.0345 gram of manganese carbonate（MnCO3）, above material purity is more than 99%.By above-mentioned raw materials mixture in agate mortar
In be fully ground, be well mixed raw material.Resulting presoma is positioned in corundum crucible, in the reduction that activated carbon is provided
Under atmosphere, with 10 DEG C of min in one fluidization atmosphere furnace-1Speed be warming up to 900 DEG C, constant temperature 6h is subsequently cooled to room temperature.Will
Presoma regrinding after calcining, in activated carbon and H2/N2（5%/95%）Integrated atmosphere furnace is provided under the reducing atmosphere of offer
In, with 10 DEG C of min-1Speed be warming up to 1300 °C, then constant temperature 8h cools to room temperature with the furnace.Taking-up is pulverized, and is obtained final product
To required fluorescent material sample.
Under 340 nm burst of ultraviolel, fluorescent material produces three broad emission bands of the nm from 380 nm to 750 to the fluorescent material,
Emission spectrum covers whole visible region, can obtain the white light of high color rendering index (CRI).The fluorescent material can be by from 260 nm to 400
The ultraviolet excitation of nm, is suitable for the new phosphorses of the white light LEDs application that UV LED chip is excited, the XRD of the fluorescent material
Figure is similar with Fig. 2, and obtained fluorescent material is garnet structure.
Embodiment 3：Mg0.88Y1.46La0.5Al4SiO12:0.03Eu2+,0.04Ce3+,0.09Mn2+The preparation of fluorescent material
Preparation method is as follows：
0.1774 gram of magnesia is weighed respectively（MgO）, 0.9228 gram of yittrium oxide（Y2O3）, 0.4073 gram of lanthana（La2O3 ） 、
1.0196 gram aluminum oxide（Al2O3）, 0.3004 gram of silica（SiO2）, 0.0264 gram of europium oxide（Eu2O3）, 0.0344 gram of cerium oxide
And 0.0519 gram of manganese carbonate（MnCO3）, above material purity is more than 99%.By above-mentioned raw materials mixture in agate mortar
In be fully ground, be well mixed raw material.Resulting presoma is positioned in corundum crucible, in the reduction that activated carbon is provided
Under atmosphere, 900 DEG C are warming up to the speed of 10 °C of min-1 in one fluidization atmosphere furnace, constant temperature 6h is subsequently cooled to room temperature.Will
Presoma regrinding after calcining, in activated carbon and H2/N2（5%/95%）Integrated atmosphere is provided under the reducing atmosphere of offer
In stove, 1300 DEG C are warming up to the speed of 10 DEG C of min-1, then constant temperature 8h cools to room temperature with the furnace.Taking-up is pulverized, i.e.,
Obtain required fluorescent material sample.
Under 340 nm burst of ultraviolel, fluorescent material produces three broad emission bands of the nm from 380 nm to 750 to the fluorescent material,
Emission spectrum covers whole visible region, can obtain the white light of high color rendering index (CRI).The fluorescent material can be by from 260 nm to 400
The ultraviolet excitation of nm, is suitable for the new phosphorses of the white light LEDs application that UV LED chip is excited, the XRD of the fluorescent material
Figure is similar with Fig. 2, and obtained fluorescent material is garnet structure.
Embodiment 4：Mg0.67Sr0.2Y1.44Gd0.5Al4SiO12:0.01Eu2+,0.06Ce3+,0.12Mn2+The preparation of fluorescent material
Preparation method is as follows：
0.1350 gram of magnesia is weighed respectively（MgO）, 0.1476g strontium carbonates（SrCO3）, 0.8129 gram of yittrium oxide（Y2O3）、
0.4531g gadolinium oxides（Gd2O3）, 1.0197 grams of aluminum oxide（Al2O3）, 0.3005 gram of silica（SiO2）, 0.0089 gram of europium oxide
（Eu2O3）, 0.0518 gram of cerium oxide and 0.0690 gram of manganese carbonate（MnCO3）, above material purity is more than 99%.Will be above-mentioned
Raw mixture is fully ground in agate mortar, is well mixed raw material.Resulting presoma is positioned over into corundum crucible
In, under the reducing atmosphere that activated carbon is provided, 900 DEG C are warming up to the speed of 10 DEG C of min-1 in one fluidization atmosphere furnace, perseverance
Warm 6h, is subsequently cooled to room temperature.Presoma after calcining is regrind, in activated carbon and H2/N2（5%/95%）What is provided goes back
During integrated atmosphere furnace is put under Primordial Qi atmosphere, with the speed of 10 DEG C of min-1 1300 DEG C are warming up to, constant temperature 8h, then along with the furnace cooling
To room temperature.Taking-up is pulverized, that is, obtain required fluorescent material sample.
Under 340 nm burst of ultraviolel, fluorescent material produces three broad emission bands of the nm from 380 nm to 750 to the fluorescent material,
Emission spectrum covers whole visible region, can obtain the white light of high color rendering index (CRI).The fluorescent material can be by from 260 nm to 400
The ultraviolet excitation of nm, is suitable for the new phosphorses of the white light LEDs application that UV LED chip is excited, the XRD of the fluorescent material
Figure is similar with Fig. 2, and obtained fluorescent material is garnet structure.
Embodiment 5：Mg0.64Ca0.1Sr0.1Y1.91Al4SiO12:0.01Eu2+,0.09Ce3+,0.15Mn2+The preparation of fluorescent material
Preparation method is as follows：
0.1290 gram of magnesia is weighed respectively（MgO）, 0.05 gram of calcium carbonate（CaCO3), 0.0738 gram of strontium carbonate（SrCO3）、
1.0782 gram yttria（Y2O3）, 1.0199 grams of alundum (Al2O3)s（Al2O3）, 0.3005 gram of silica（SiO2）、
0.0090 gram of europiumsesquioxide（Eu2O3）, 0.0774 gram of ceria and 0.0865 gram of manganese carbonate（MnCO3）, above raw material is pure
Degree is more than 99%.Above-mentioned raw materials mixture is fully ground in agate mortar, raw material is well mixed.Will be resulting
Presoma is positioned in corundum crucible, under the reducing atmosphere that activated carbon is provided, with 10 DEG C of min-1 in one fluidization atmosphere furnace
Speed be warming up to 900 DEG C, constant temperature 6h is subsequently cooled to room temperature.Presoma after calcining is regrind, in activated carbon and
H2/N2（5%/95%）During integrated atmosphere furnace is provided under the reducing atmosphere of offer, with the speed of 10 DEG C of min-1 1300 are warming up to
DEG C, then constant temperature 8h cools to room temperature with the furnace.Taking-up is pulverized, that is, obtain required fluorescent material sample.
Under 340 nm burst of ultraviolel, fluorescent material produces three broad emission bands of the nm from 380 nm to 750 to the fluorescent material,
Emission spectrum covers whole visible region, can obtain the white light of high color rendering index (CRI).The fluorescent material can be by from 260 nm to 400
The ultraviolet excitation of nm, is suitable for the new phosphorses of the white light LEDs application that UV LED chip is excited, the XRD of the fluorescent material
Figure is similar with Fig. 2, and obtained fluorescent material is garnet structure.
Embodiment 6：
Mg0.95Y1.94Ga4SiO12:0.02Eu3+、0.06Ce3+、0.03Mn2+The preparation of fluorescent material.
Preparation method is as follows：
0.1915 gram of magnesia is weighed respectively（MgO）, 1.0952 grams of yittrium oxide（Y2O3）, 1.8744 grams of gallium oxides（Ga2O3）、
0.3004 gram of silica（SiO2）, 0.0176 gram of urania（Eu2O3）, 0.0516 gram of cerium oxide（CeO2）, 0.0172 gram of manganese carbonate
（MnCO3）Above material purity is more than 99%.Above-mentioned raw materials mixture is fully ground in agate mortar, raw material is mixed
Close uniform.Resulting presoma is positioned in corundum crucible, under the reducing atmosphere that activated carbon is provided, in integrated atmosphere
900 DEG C are warming up to the speed of 10 DEG C of min-1 in stove, constant temperature 6h is subsequently cooled to room temperature.By the presoma after calcining again
Grinding, in activated carbon and H2/N2（5%/95%）During integrated atmosphere furnace is put under the reducing atmosphere of offer, with 10 DEG C of min-1's
Speed is warming up to 1300 DEG C, and then constant temperature 8h cools to room temperature with the furnace.Taking-up is pulverized, that is, obtain required fluorescent material sample.
Under 340 nm burst of ultraviolel, fluorescent material produces three broad emission bands of the nm from 380 nm to 750 to the fluorescent material,
Emission spectrum covers whole visible region, can obtain the white light of high color rendering index (CRI).The fluorescent material can be by from 260 nm to 400
The ultraviolet excitation of nm, is suitable for the new phosphorses of the white light LEDs application that UV LED chip is excited, the XRD of the fluorescent material
Figure is similar with Fig. 2, and obtained fluorescent material is garnet structure.
Embodiment 7：
Mg0.93Y1.97Al4Si0.7Ge0.3O12:0.01Eu2+,0.03Ce3+,0.06Mn2+The preparation of fluorescent material
Preparation method is as follows：
0.1874 gram of magnesia is weighed respectively（MgO）, 1.1121 grams of yittrium oxide（Y2O3）, 1.0196 grams of aluminum oxide（Al2O3）、
0.2103 gram of silica（SiO2）, 0.1570 gram of germanium oxide（GeO2）, 0.0088 gram of europium oxide（Eu2O3）, 0.0258 gram of cerium oxide
And 0.0345 gram of manganese carbonate（MnCO3）, above material purity is more than 99%.By above-mentioned raw materials mixture in agate mortar
In be fully ground, be well mixed raw material.Resulting presoma is positioned in corundum crucible, in the reduction that activated carbon is provided
Under atmosphere, 900 DEG C are warming up to the speed of 10 DEG C of min-1 in one fluidization atmosphere furnace, constant temperature 6h is subsequently cooled to room temperature.Will
Presoma regrinding after calcining, in activated carbon and H2/N2（5%/95%）Integrated atmosphere is provided under the reducing atmosphere of offer
In stove, 1300 DEG C are warming up to the speed of 10 DEG C of min-1, then constant temperature 8h cools to room temperature with the furnace.Taking-up is pulverized, i.e.,
Obtain required fluorescent material sample.
Under 340 nm burst of ultraviolel, fluorescent material produces three broad emission bands of the nm from 380 nm to 750 to the fluorescent material,
Emission spectrum covers whole visible region, can obtain the white light of high color rendering index (CRI).The fluorescent material can be by from 260 nm to 400
The ultraviolet excitation of nm, is suitable for the new phosphorses of the white light LEDs application that UV LED chip is excited, the XRD of the fluorescent material
Figure is similar with Fig. 2, and obtained fluorescent material is garnet structure.
Embodiment 8：
Mg0.71Ca0.2Y1.44Gd0.5Al4Si0.7Ge0.3O12:0.03Eu2+,0.06Ce3+,0.06Mn2+The preparation of fluorescent material
Preparation method is as follows：
0.1431 gram of magnesia is weighed respectively（MgO）, 0.1001 gram of calcium carbonate（CaCO3), 0.8129 gram of yittrium oxide（Y2O3）、
0.9063 gram of gadolinium oxide（Gd2O3), 1.0196 grams of aluminum oxide（Al2O3）, 0.2103 gram of silica（SiO2）, 0.1570 gram of germanium oxide
（GeO2）, 0.0264 gram of europium oxide（Eu2O3）, 0.0516 gram of cerium oxide and 0.0345 gram of manganese carbonate（MnCO3）, above raw material
Purity is more than 99%.Above-mentioned raw materials mixture is fully ground in agate mortar, raw material is well mixed.Will be resulting
Presoma be positioned in corundum crucible, activated carbon provide reducing atmosphere under, with 10 DEG C of min- in one fluidization atmosphere furnace
1 speed is warming up to 900 DEG C, and constant temperature 6h is subsequently cooled to room temperature.Presoma after calcining is regrind, in activated carbon and
H2/N2（5%/95%）During integrated atmosphere furnace is provided under the reducing atmosphere of offer, with the speed of 10 DEG C of min-1 1300 are warming up to
DEG C, then constant temperature 8h cools to room temperature with the furnace.Taking-up is pulverized, that is, obtain required fluorescent material sample.
Under 340 nm burst of ultraviolel, fluorescent material produces three broad emission bands of the nm from 380 nm to 750 to the fluorescent material,
Emission spectrum covers whole visible region, can obtain the white light of high color rendering index (CRI).The fluorescent material can be by from 260 nm to 400
The ultraviolet excitation of nm, is suitable for the new phosphorses of the white light LEDs application that UV LED chip is excited, the XRD of the fluorescent material
Figure is similar with Fig. 2, and obtained fluorescent material is garnet structure.
Claims (10)
1. a kind of garnet structure single-substrate white fluorescent powder, it is characterised in that the chemical expression of the fluorescent material is：
Mg1-a-x-zAaY2-b-yBbAl4-cCcSi1-dDdO12:xEu3+,yCe3+,zMn2+
In formula：A is the combination of one or two arbitrary proportions in Sr, Ca, and B is one or more in Gd, La, Lu
The combination of arbitrary proportion；C is Ga；D is Ge；X, y, z, a, b, c, d are respective molar fraction, and their span is divided
It is not： 0≤a≤0.2；0≤b≤0.5；0≤c≤4；0≤d≤0.3；0.005≤x≤0.10；0.005≤y≤0.12；
0.005≤z≤0.15。
2. a kind of garnet structure single-substrate white fluorescent powder according to claim 1, it is characterised in that 0.01≤x≤
0.10；0.03≤y≤0.09；0.03≤z≤0.15.
3. a kind of garnet structure single-substrate white fluorescent powder according to claim 1, it is characterised in that A is Ca, and B is
La。
4. according to a kind of arbitrary described garnet structure single-substrate white fluorescent powder of claim 1-3, it is characterised in that Mg1-x- zY2-yAl4SiO12:xEu3+,yCe3+,zMn2+。
5. a kind of preparation method of the garnet structure single-substrate white fluorescent powder according to claim 1, including following step
Suddenly：
1）By described chemical expression Mg1-a-x-zAaY2-b-yBbAl4-cCcSi1-dDdO12:xEu3+,yCe3+,zMn2+In each unit
The compound of element is raw material, and by the molar ratio of each element in the chemical expression each raw material of respective quality is weighed respectively,
Each raw material solid powder mull is mixed into obtain presoma；
2）By step 1）The presoma for obtaining is placed in reducing atmosphere, is warming up to 900 DEG C～1500 DEG C roasting temperatures 1 ~ 5
It is secondary, obtain final product of roasting；Every time roasting time is 5 ~ 24 hours, is cooled to room temperature between every double roasting and is ground place
Reason, last time roasting carries out under reducing atmosphere, the reducing atmosphere be the nitrogen mixture containing 5-10v% hydrogen or
Nitrogen mixture containing 5-10v% carbon monoxide；
3）By step 2) final product of roasting Jing is broken, levigate, grain size grading, and scrubbed removal of impurities, drying be obtained described in
Garnet structure single-substrate white fluorescent powder.
6. the preparation method of the garnet structure single-substrate white fluorescent powder according to claim 5, it is characterised in that step
2）Presoma be placed on roasting 1 ~ 2 time in reducing atmosphere.
7. the preparation method of the garnet structure single-substrate white fluorescent powder according to claim 5, it is characterised in that step
2）The heating rate for being warming up to 900 DEG C～1500 DEG C is 5 DEG C/min～20 DEG C/min.
8. the preparation method of the garnet structure single-substrate white fluorescent powder according to claim 5, it is characterised in that step
2）Middle grinding is carried out in agate mortar or ball mill.
9. the preparation method of the garnet structure single-substrate white fluorescent powder according to claim 5, it is characterised in that step
3）In final product of roasting adopt after hand-crushed and to make the particle size of sintered body levigate with ball milling method again, Jing sedimentation, sieve
Point-score or air-flow method are classified, and take the pressed powder that granularity is 3 ~ 10 microns, are washed 1-4 time with water or methyl alcohol, filter to isolate solid
Phase, in 110 DEG C ~ 130 DEG C 2-6 h are dried.
10. application of the garnet structure single-substrate white fluorescent powder according to claim 1 in white light LEDs.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111120A (en) * | 2018-10-26 | 2019-01-01 | 浙江工业大学 | A kind of warm white LED is with can spontaneous crystallization fluorescent glass-ceramics and preparation method thereof |
| CN110724530A (en) * | 2019-10-31 | 2020-01-24 | 广东省稀有金属研究所 | Near-infrared long-afterglow luminescent material, preparation method and application thereof |
| CN112391166A (en) * | 2020-11-20 | 2021-02-23 | 南京林业大学 | Ce3+-Mn2+Co-activated efficient near-infrared fluorescent powder and preparation method and application thereof |
| CN113150783A (en) * | 2021-04-27 | 2021-07-23 | 中国科学院长春应用化学研究所 | Color-adjustable afterglow luminescent material, preparation method thereof and lighting product |
| CN115305088A (en) * | 2022-08-22 | 2022-11-08 | 杭州爱视芙健康科技有限公司 | Garnet structure-derived fluorescent powder material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1955116A (en) * | 2005-10-24 | 2007-05-02 | 富士胶片株式会社 | Inorganic compound, composition and molded body containing the same, light emitting device, and solid laser device |
| US20110279022A1 (en) * | 2008-10-13 | 2011-11-17 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Doped garnet fluorescent substance having red shift for pc leds |
| CN103003389A (en) * | 2010-07-21 | 2013-03-27 | 默克专利有限公司 | Aluminate luminescent substances |
| CN104212458A (en) * | 2014-08-11 | 2014-12-17 | 浙江工业大学 | Red and orange light fluorescent powder with garnet structure and preparation method thereof |
-
2016
- 2016-12-02 CN CN201611095388.3A patent/CN106635014A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1955116A (en) * | 2005-10-24 | 2007-05-02 | 富士胶片株式会社 | Inorganic compound, composition and molded body containing the same, light emitting device, and solid laser device |
| US20110279022A1 (en) * | 2008-10-13 | 2011-11-17 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Doped garnet fluorescent substance having red shift for pc leds |
| CN103003389A (en) * | 2010-07-21 | 2013-03-27 | 默克专利有限公司 | Aluminate luminescent substances |
| CN104212458A (en) * | 2014-08-11 | 2014-12-17 | 浙江工业大学 | Red and orange light fluorescent powder with garnet structure and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| CHANGHUA ZHANG等: "A single-phase Ba9Lu2Si6O24:Eu2+, Ce3+, Mn2+ phosphor with tunable full-color emission for NUV-based white LED applications", 《MATERIALS RESEARCH BULLETIN》 * |
| LIU BIAN等: "Energy transfer and color tuning in the Ba9Sc2Si6O24:Ce3+,Eu2+,Mn2+ phosphor", 《RSC ADVANCES》 * |
| ZAIFA PAN等: "Structure and redshift of Ce3+ emission in anisotropically expanded garnet phosphor MgY2Al4SiO12:Ce3+", 《RSC ADVANCES》 * |
| ZHANG ZHENG等: "Tunable luminescence and energy transfer of Ce3+/Eu2+/Mn2+ tridoped Sr8MgLa(PO4)7 phosphor for white light LEDs", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111120A (en) * | 2018-10-26 | 2019-01-01 | 浙江工业大学 | A kind of warm white LED is with can spontaneous crystallization fluorescent glass-ceramics and preparation method thereof |
| CN109111120B (en) * | 2018-10-26 | 2021-09-21 | 浙江工业大学 | Spontaneous crystallization fluorescent microcrystalline glass for warm white LED and preparation method thereof |
| CN110724530A (en) * | 2019-10-31 | 2020-01-24 | 广东省稀有金属研究所 | Near-infrared long-afterglow luminescent material, preparation method and application thereof |
| CN110724530B (en) * | 2019-10-31 | 2022-05-17 | 广东省稀有金属研究所 | Near-infrared long-afterglow luminescent material, preparation method and application thereof |
| CN112391166A (en) * | 2020-11-20 | 2021-02-23 | 南京林业大学 | Ce3+-Mn2+Co-activated efficient near-infrared fluorescent powder and preparation method and application thereof |
| CN113150783A (en) * | 2021-04-27 | 2021-07-23 | 中国科学院长春应用化学研究所 | Color-adjustable afterglow luminescent material, preparation method thereof and lighting product |
| CN113150783B (en) * | 2021-04-27 | 2022-11-01 | 中国科学院长春应用化学研究所 | Color-adjustable afterglow luminescent material, preparation method thereof and lighting product |
| CN115305088A (en) * | 2022-08-22 | 2022-11-08 | 杭州爱视芙健康科技有限公司 | Garnet structure-derived fluorescent powder material and preparation method and application thereof |
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