CN116144357B - Ultraviolet excited green light emitting fluorescent powder and preparation method and application thereof - Google Patents
Ultraviolet excited green light emitting fluorescent powder and preparation method and application thereof Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 17
- 229910006404 SnO 2 Inorganic materials 0.000 claims abstract description 17
- 108010043121 Green Fluorescent Proteins Proteins 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 230000005284 excitation Effects 0.000 claims description 9
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 6
- 230000003595 spectral effect Effects 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 230000036541 health Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 229910001887 tin oxide Inorganic materials 0.000 claims 1
- 238000001228 spectrum Methods 0.000 abstract description 16
- 238000000295 emission spectrum Methods 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910052733 gallium Inorganic materials 0.000 abstract description 5
- 229910052738 indium Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000011068 loading method Methods 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 150000004767 nitrides Chemical class 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 238000009877 rendering Methods 0.000 description 4
- 238000005090 crystal field Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000012190 activator Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 rare earth ion Chemical class 0.000 description 2
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77342—Silicates
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
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- 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
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
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Abstract
The invention relates to ultraviolet excited green light emitting fluorescent powder and a preparation method and application thereof. Which is ultraviolet excited Eu 2+ Doped green fluorescent powder belonging to AO-B 2 O 3 ‑SnO 2 ‑SiO 2 -a EuO system, wherein a is one or several of Ca, sr or Ba; b is one or more of Ga or In, and the components of the B are as follows In mass percent of each oxide: AO is more than or equal to 20.41 percent and less than or equal to 41.2 percent, B is more than or equal to 18.31 percent 2 O 3 ≤33.76％，20.29％≤SnO 2 ≤30.88％，13.48％≤SiO 2 Less than or equal to 20.52 percent, 0.11 percent and less than or equal to 0.384 percent of EuO. Compared with the prior art, the fluorescent powder disclosed by the invention is oxide-based fluorescent powder, has the outstanding advantages of stable physical and chemical properties, simplicity and convenience in preparation, low cost and the like, has the emission wavelength of 435-650 nm, belongs to broadband emission, can effectively absorb light in the wavelength range of 200-480 nm, has the characteristic of wide emission spectrum range, and is suitable for application of ultraviolet chip white light LEDs, ultraviolet chip solar light LEDs, ultraviolet chip full-spectrum LEDs, ultraviolet chip high-quality white light LEDs and the like.
Description
Technical Field
The invention belongs to the technical field of fluorescent powder preparation, and particularly relates to ultraviolet excited green light emitting fluorescent powder and a preparation method and application thereof.
Background
White light emitting diodes (W-LEDs) have received a great deal of attention for their advantages of environmental protection, high efficiency, long life, energy saving, etc., and have gradually become the mainstream illumination sources in the current market. The common method for realizing white light at present is to combine an InGaN blue light chip with yellow fluorescent powder Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce 3+ ) And (3) combining. However, the color rendering index is low, the color temperature is high, and the strong peak of the blue light chip exists, so that the proportion of the luminous intensity is unbalanced, and the blue light chip is not suitable for healthy illumination, so that the application of the blue light chip in the indoor illumination field is limited. In order to produce high quality white light, near ultraviolet (n-UV) LED chips combined with trichromatic (red, green, blue) phosphors are a promising approach. The emission wavelength of the InGaN chip has gradually developed to near ultraviolet region, which can provide larger excitation energy for fluorescent material, and further improve the light intensity of white light LED. And because ultraviolet light is invisible, the three-color (red, green and blue) fluorescent powder plays an important role in the color stability and the color rendering index of the white light LED, and the green fluorescent powder is indispensable in reducing the color temperature of the white light, improving the color rendering property and the like.
Meanwhile, with the development of LEDs, higher requirements are put on the cost and stability of fluorescent conversion materials, and although a great deal of work has been done in the aspect of exploring and researching green-emitting fluorescent powder, rare earth ion doped broadband green-emitting fluorescent powder is still less obtained at present due to the limitations of crystal field intensity and coordination ions. Among the existing green phosphors, nitride materials such as Eu are currently commonly used 2+ Doped nitride beta-SiAlON Eu 2+ The fluorescent powder is high-efficiency green light fluorescent powder excited by a near ultraviolet LED, but the preparation condition of the nitride fluorescent powder is severe, the raw materials of the nitride fluorescent powder are expensive, and the further application of the nitride fluorescent powder in a white light LED is limited. Thus, the oxide is widely paid attention to because of its simple preparation method and stable physicochemical properties. Therefore, development of an oxide-based broadband green phosphor capable of being excited by near ultraviolet and excellent in performance is critical to development of white LEDs.
The luminescence characteristics of the phosphor are largely dependent on the crystal structure of the host material, and variations in the structure are liable to affect the energy transfer process, crystal field strength, and covalent properties. Therefore Eu 2+ The green light emitted by the doped phosphor begins to enter the human field of view, while Eu 2+ Is a rare earth ion with excellent luminescence property and 4f n-1 5d 1 Outer layer electronic configuration, 5d track bareExposed to the outer layer, under the action of local vibration of the crystal lattice of the matrix, 4f 6 5d 1 The split energy level becomes continuous energy band, so that the emission spectrum type is broadband emission, the intensity is higher, the fluorescence lifetime is shorter, the property of the broadband emission can just meet the requirements of white light LEDs, sunlight-like LEDs, full spectrum LEDs, high color rendering white light LEDs and the like on spectrum continuity, no light spectrum deletion and the like, and the broadband emission spectrum type rare earth activator has become a widely used rare earth activator. By changing Eu 2+ Concentration and reducing atmosphere of (a) to affect Eu 2+ And the surrounding crystal field environment realizes the continuous regulation and control of the luminous color. And the spectrum can be changed significantly with the composition and structure of the matrix material, so Eu 2+ Ions have become important candidate doping ions for rare earth doped phosphors.
Disclosure of Invention
Eu based on oxide based ultraviolet excitation in the prior art 2+ The invention provides ultraviolet excited green light emitting fluorescent powder and a preparation method and application thereof, which meet the urgent requirements of the current white light LED/solar light LED-like light LED/full spectrum LED/healthy illumination LED light source.
The aim of the invention can be achieved by the following technical scheme:
the invention provides an ultraviolet excited green light emitting fluorescent powder which is ultraviolet excited Eu 2+ Doped green fluorescent powder belonging to AO-B 2 O 3 -SnO 2 -SiO 2 -a EuO system, wherein a is one or several of Ca, sr or Ba; b is one or more of Ga or In, and the components of the B are as follows In mass percent of each oxide: AO is more than or equal to 20.41 percent and less than or equal to 41.2 percent, B is more than or equal to 18.31 percent 2 O 3 ≤33.76％，20.29％≤SnO 2 ≤30.88％，13.48％≤SiO 2 ≤20.52％，0.11％≤EuO≤0.384％。
In one embodiment of the invention, the ultraviolet excited green light emitting fluorescent powder can emit green light with a spectrum range covering 435-650 nm and a center wavelength of 507nm under ultraviolet excitation, belongs to broadband emission, and can effectively absorb light with a wavelength range of 200-480 nm.
Preferably, the phosphor is AO-B 2 O 3 -SnO 2 -SiO 2 -a EuO system, wherein a is one or several of Ca, sr or Ba; b is one or more systems of Ga or In, and the mol ratio of the component A to the component B to the component Sn to the component Si to the component Eu is=2.98-2.993:2:1.5:2.5:0.007-0.02.
Still further preferably, the phosphor is AO-B 2 O 3 -SnO 2 -SiO 2 -a EuO system, wherein a is one or several of Ca, sr or Ba; b is one or more of Ga or In, and the mol ratio of component A to Sn to Si is=2.993:2:1.5:2.5:0.007, or the mol ratio of component A to Sn to Si is=2.99:2:1.5:2.5:0.01, or the mol ratio of component A to Sn to Si is=2.985:2:1.5:2.5:0.015, or the mol ratio of component A to Sn to Si is=2.98:2:1.5:2.5:0.02.
The invention further provides a preparation method of the ultraviolet excited green light emitting fluorescent powder, which comprises the following steps:
(1) Weighing a proper amount of a compound containing A, a compound containing B, a compound containing Sn, a compound containing Si and a compound containing Eu as raw material powder;
(2) Grinding and uniformly mixing the mixture obtained in the step (1);
(3) Placing the ground raw material powder into an alumina crucible, calcining the alumina crucible filled with the raw material in an air atmosphere, and naturally cooling to room temperature;
(4) And (3) sufficiently grinding the mixed product obtained after calcining in the step (3) uniformly again, placing the mixed product in a reducing atmosphere mixed with hydrogen and nitrogen for sintering, and then cooling to room temperature to finally obtain the ultraviolet excited green light emitting fluorescent powder.
In some embodiments of the invention, the compound containing a In step (1) is an oxide, halide or carbonate of Ca, sr or Ba, the compound containing B is an oxide or halide of Ga and In, the compound containing Sn is an oxide containing Sn, the compound containing Si is an oxide containing Si, silicate or silicic acid, and the compound containing Eu is an oxide or halide containing Eu.
In some embodiments of the present invention, the weighed a-containing compound, B-containing compound, sn-containing compound, si-containing compound, and Eu-containing compound described in step (1) may be in an appropriate excess.
In some embodiments of the invention, the milling in step (2) and step (4) is performed for a period of 20 to 50 minutes.
In some embodiments of the invention, the sintering temperature in the air atmosphere described in step (2) is 300 to 1000 ℃ and the sintering time is 5 to 20 hours.
In some embodiments of the invention, the reduction sintering temperature in step (4) is 1100 to 1400 ℃ and the sintering time is 8 to 20 hours.
In some embodiments of the invention, the reduction sintering described in step (4) is 5%H 2 -95％N 2 Is reduced in a hydrogen-nitrogen mixed atmosphere.
The invention further provides application of the ultraviolet excited green light emitting fluorescent powder, and the ultraviolet excited green light emitting fluorescent powder is used for preparing an ultraviolet chip white light LED, an ultraviolet chip solar light LED, an ultraviolet chip full spectrum LED or an ultraviolet chip health lighting LED.
The fluorescent powder is oxide-based fluorescent powder, has the outstanding advantages of stable physical and chemical properties, simple and convenient preparation, low cost and the like, has the emission wavelength of 435-650 nm, belongs to broadband emission, can effectively absorb light in the wavelength range of 200-480 nm, has the characteristic of wide emission spectrum range, and is suitable for application of ultraviolet chip white light LEDs, ultraviolet chip solar light LEDs, ultraviolet chip full spectrum LEDs, ultraviolet chip high-quality white light LEDs and the like.
Compared with the prior art, the invention has the advantages and beneficial effects that:
(1) The fluorescent powder can emit green light with a spectral range covering 435-650 nm and a central wavelength of 507nm under ultraviolet excitation, and is not reported.
(2) Compared with the prior art, the fluorescent powder is Eu 2+ The doped oxide-based green light emitting fluorescent powder has the advantage of stable physicochemical property, and meanwhile, the fluorescent powder can adopt a conventional solid phase reaction methodThe prepared material has the characteristics of simple preparation process and contribution to industrial production, is good, and can be widely applied candidate materials.
(3) The fluorescent powder can be well matched with the existing commercial near ultraviolet LED chip, and is suitable for application of ultraviolet chip white light LEDs, ultraviolet chip solar light LEDs, ultraviolet chip full spectrum LEDs, ultraviolet chip high-quality white light LEDs and the like.
Drawings
Fig. 1 is a photo-excitation-emission spectrum of example 1 of the present invention.
Fig. 2 shows photoluminescence spectra of examples 1, 2 and 3 according to the present invention.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1:
1. SrCO is selected for use 3 、Ga 2 O 3 、SnO 2 、SiO 2 、Eu 2 O 3 As starting materials, five materials were weighed respectively corresponding to x=0.007 (molar ratio) and mixed materials were controlled to have a total mass of 20g in the raw material mixture.
2. Grinding the raw material mixture in an agate mortar for 20 to 50 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, calcining the alumina crucible filled with the raw material at 300 ℃ for 5 hours in an air atmosphere, and naturally cooling to room temperature; and then, after the obtained mixed product is sufficiently and uniformly ground again, placing the mixed product in a reducing atmosphere mixed with hydrogen and nitrogen, calcining at 1100 ℃ for 8 hours, and then cooling to room temperature to obtain the target product.
3. The spectral properties of the phosphor of this system were tested using a fluorescence spectrometer (HITACHI F-7000), as shown in FIGS. 1 and 2. The result shows that the fluorescent powder of the system has wider excitation band, covers ultraviolet, purple light and blue light areas (200-480 nm), has a peak value near 357nm and a higher spectrum peak value, and can be effectively excited by ultraviolet and purple light chips and well matched with an n-UV LED chip. Under the excitation of 357nm ultraviolet light source, the fluorescent powder emits bright green light, and the emission spectrum is composed of a wider emission band (435-650 nm), and the peak value is located at 507nm.
Example 2:
1. SrCO is selected for use 3 、Ga 2 O 3 、SnO 2 、SiO 2 、Eu 2 O 3 As starting materials, five materials were weighed respectively corresponding to x=0.01, and the total mass of the raw material mixture was controlled to be 20g of mixed raw material.
2. Grinding the raw material mixture in an agate mortar for 20 to 50 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, calcining the alumina crucible filled with the raw material at 500 ℃ for 10 hours in an air atmosphere, and naturally cooling to room temperature; and then, after the obtained mixed product is sufficiently and uniformly ground again, placing the mixed product in a reducing atmosphere mixed with hydrogen and nitrogen, calcining the mixed product at 1200 ℃ for 12 hours, and then cooling the mixed product to room temperature to obtain the target product.
3. The spectral properties of the phosphor of this system were tested using a fluorescence spectrometer (HITACHI F-7000), as shown in FIG. 2. The result shows that the fluorescent powder of the system emits bright green light under the excitation of an ultraviolet light source with the wavelength of 357nm, and the emission spectrum is composed of a wider emission band (435-650 nm), and the peak value is positioned at 507nm.
Example 3:
1. SrCO is selected for use 3 、Ga 2 O 3 、SnO 2 、SiO 2 、Eu 2 O 3 As starting materials, five materials were weighed respectively corresponding to x=0.015 and mixed materials were controlled to have a total mass of 20g in the raw material mixture.
2. Grinding the raw material mixture in an agate mortar for 20 to 50 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, calcining the alumina crucible filled with the raw material at 700 ℃ for 16 hours in an air atmosphere, and naturally cooling to room temperature; and (3) sufficiently grinding the obtained mixed product again uniformly, placing the mixed product in a reducing atmosphere mixed with hydrogen and nitrogen, calcining at 1300 ℃ for 16 hours, and cooling to room temperature to obtain the target product.
3. The spectral properties of the phosphor of this system were tested using a fluorescence spectrometer (HITACHI F-7000), as shown in FIG. 2. The result shows that the fluorescent powder of the system emits bright green light under the excitation of an ultraviolet light source with the wavelength of 357nm, and the emission spectrum is composed of a wider emission band (435-650 nm), and the peak value is positioned at 507nm.
Example 4:
1. SrCO is selected for use 3 、Ga 2 O 3 、SnO 2 、SiO 2 、Eu 2 O 3 As starting materials, five materials were weighed respectively corresponding to x=0.02, and the total mass of the raw material mixture was controlled to be 20g of mixed raw material.
2. Grinding the raw material mixture in an agate mortar for 20 to 50 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, calcining the alumina crucible filled with the raw material at 900 ℃ for 18 hours in an air atmosphere, and naturally cooling to room temperature; after the obtained mixed product was sufficiently ground again to uniformity, it was calcined at 1400 ℃ for 20 hours in a reducing atmosphere mixed with hydrogen and nitrogen, and then cooled to room temperature, to obtain the objective product, the fluorescent spectrum properties of which were similar to those of example 1.
Example 5:
1. BaCO is selected for use 3 、Ga 2 O 3 、SnO 2 、SiO 2 、Eu 2 O 3 As starting materials, ba: ga: sn: si: eu=2.993:2:1.5:2.5:0.007 (molar ratio), corresponding to x=0.007, five materials were weighed respectively, and the total mass of the raw material mixture was controlled to be 20g of mixed raw material.
2. Grinding the raw material mixture in an agate mortar for 20 to 50 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, calcining the alumina crucible filled with the raw material at 700 ℃ for 8 hours in an air atmosphere, and naturally cooling to room temperature; after the obtained mixed product was sufficiently ground again to uniformity, it was calcined at 1350 ℃ for 10 hours in a reducing atmosphere mixed with hydrogen and nitrogen, and then cooled to room temperature, to obtain the objective product, the fluorescent spectrum properties of which were similar to those of example 1.
Example 6:
1. CaCO is selected for use 3 、Ga 2 O 3 、SnO 2 、SiO 2 、Eu 2 O 3 As starting materials, ca: ga: sn: eu=2.993:2:1.5:2.5:0.007 (molar ratio), corresponding to x=0.007, five materials were weighed respectively, and the total mass of the raw material mixture was controlled to be 20g of mixed raw material.
2. Grinding the raw material mixture in an agate mortar for 20 to 50 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, calcining the alumina crucible filled with the raw material at 800 ℃ for 8 hours in an air atmosphere, and naturally cooling to room temperature; after the obtained mixed product was sufficiently ground again to uniformity, it was calcined at 1400 ℃ for 10 hours in a reducing atmosphere mixed with hydrogen and nitrogen, and then cooled to room temperature, to obtain the objective product, the fluorescent spectrum properties of which were similar to those of example 1.
Example 7:
1. SrCO is selected for use 3 、In 2 O 3 、SnO 2 、SiO 2 、Eu 2 O 3 As starting materials, sr: in: sn: si: eu=2.993:2:1.5:2.5:0.007 (molar ratio), five materials were weighed respectively corresponding to x=0.007, and the total mass of the raw material mixture was controlled to be 20g of mixed raw material.
2. Grinding the raw material mixture in an agate mortar for 20 to 50 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, calcining the alumina crucible filled with the raw material at 600 ℃ for 8 hours in an air atmosphere, and naturally cooling to room temperature; after the obtained mixed product was sufficiently ground again, it was calcined at 1300 ℃ for 10 hours in a reducing atmosphere mixed with hydrogen and nitrogen, and then cooled to room temperature, to obtain the objective product, the fluorescence spectrum properties of which were similar to those of example 1.
Example 8:
1. BaCO is selected for use 3 、In 2 O 3 、SnO 2 、SiO 2 、Eu 2 O 3 As starting materials, ba: in: sn: si: eu=2.992:2:1.5:2.5:0.007 (molar ratio), corresponding to x=0.007, five materials were weighed respectively, and the total mass of the raw material mixture was controlled to be 20g of mixed raw material.
2. Grinding the raw material mixture in an agate mortar for 20 to 50 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, calcining the alumina crucible filled with the raw material at 700 ℃ for 8 hours in an air atmosphere, and naturally cooling to room temperature; after the obtained mixed product was sufficiently ground again to uniformity, it was calcined at 1350 ℃ for 10 hours in a reducing atmosphere mixed with hydrogen and nitrogen, and then cooled to room temperature, to obtain the objective product, the fluorescent spectrum properties of which were similar to those of example 1.
Example 9:
1. CaCO is selected for use 3 、In 2 O 3 、SnO 2 、SiO 2 、Eu 2 O 3 As starting materials, ca: in: sn: si: eu=2.993:2:1.5:2.5:0.007 (molar ratio), corresponding to x=0.007, five materials were weighed respectively, and the total mass of the raw material mixture was controlled to be 20g of mixed raw material.
2. Grinding the raw material mixture in an agate mortar for 20 to 50 minutes, loading the mixture into an alumina crucible after the materials are uniformly mixed, calcining the alumina crucible filled with the raw material at 800 ℃ for 8 hours in an air atmosphere, and naturally cooling to room temperature; after the obtained mixed product was sufficiently ground again to uniformity, it was calcined at 1400 ℃ for 10 hours in a reducing atmosphere mixed with hydrogen and nitrogen, and then cooled to room temperature, to obtain the objective product, the fluorescent spectrum properties of which were similar to those of example 1.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (9)
1. An ultraviolet excited green light emitting phosphor characterized in that it is an ultraviolet excited Eu 2+ Doped green fluorescent powder which is AO-Ga 2 O 3 -SnO 2 -SiO 2 -a EuO system, wherein a is one or several of Ca, sr or Ba; the molar ratio of the component A to the component Ga to the component Sn to the component Si to the component Eu=2.98-2.993 to the component A is 1.5 to the component A is 2.5 to the component A is 0.007-0.02.
2. The ultraviolet excited green light emitting phosphor of claim 1, wherein the phosphor is AO-Ga 2 O 3 -SnO 2 -SiO 2 -a EuO system, wherein a is one or several of Ca, sr or Ba; the molar ratio of component A to Ga to Sn to Si to Eu= 2.993:2.5:0.007, or the molar ratio of component A to Ga to Si to Eu=2.99:2.1.5:0.01, or the molar ratio of component A to Ga to Sn to Si to Eu=2.985:2.5:1.5:2.5:0.015, or the molar ratio of component A to Ga to Sn to Si to Eu=2.98:2.5:2.5:0.02.
3. The ultraviolet excited green light emitting phosphor of claim 1 or 2, wherein the ultraviolet excited green light emitting phosphor emits green light with a spectral range covering 435-650 nm and a center wavelength at 507nm under ultraviolet excitation.
4. The method for preparing the ultraviolet excited green light emitting phosphor according to any one of claims 1 to 2, comprising the steps of:
(1) Weighing a proper amount of a compound containing A, a Ga compound, a Sn compound, a Si compound and a Eu compound as raw material powder;
(2) Grinding and uniformly mixing the mixture obtained in the step (1);
(3) Placing the ground raw material powder into an alumina crucible, calcining the alumina crucible filled with the raw material in an air atmosphere, and naturally cooling to room temperature;
(4) And (3) sufficiently grinding the mixed product obtained after calcining in the step (3) uniformly again, placing the mixed product in a reducing atmosphere mixed with hydrogen and nitrogen for sintering, and then cooling to room temperature to finally obtain the ultraviolet excited green light emitting fluorescent powder.
5. The method of producing ultraviolet excited green light-emitting phosphor according to claim 4, wherein the compound A in step (1) is an oxide, halide or carbonate of Ca, sr or Ba, the Ga-containing compound is an oxide or halide of Ga, the Sn-containing compound is an oxide of Sn, the Si-containing compound is an oxide, silicate or silicic acid containing Si, and the Eu-containing compound is an oxide or halide containing Eu.
6. The method for preparing ultraviolet excited green light emitting phosphor according to claim 4, wherein the grinding time in step (2) and step (4) is 20 to 50 min;
the sintering temperature in the air atmosphere in the step (2) is 300-1000 ℃ and the sintering time is 5-20 h.
7. The method for preparing ultraviolet excited green light emitting phosphor according to claim 4, wherein the reduction sintering temperature in the step (4) is 1100-1400 ℃ and the sintering time is 8-20 h.
8. The method of producing ultraviolet excited green light-emitting phosphor according to claim 4, wherein the reduction sintering in step (4) is 5% H 2 - 95 %N 2 Is reduced in a hydrogen-nitrogen mixed atmosphere.
9. Use of an ultraviolet excited green light emitting phosphor according to any one of claims 1-2 for the preparation of an ultraviolet chip health lighting LED.
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