CN107142106A - A kind of blue fluorescent powder for white-light LED and preparation method thereof - Google Patents
A kind of blue fluorescent powder for white-light LED and preparation method thereof Download PDFInfo
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- CN107142106A CN107142106A CN201710343597.3A CN201710343597A CN107142106A CN 107142106 A CN107142106 A CN 107142106A CN 201710343597 A CN201710343597 A CN 201710343597A CN 107142106 A CN107142106 A CN 107142106A
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- fluorescent powder
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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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7737—Phosphates
- C09K11/7738—Phosphates with alkaline earth metals
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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
- 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
Abstract
The present invention relates to rare earth luminescent material technical field.A kind of white light LEDs phosphate blue fluorescent powder, with following chemical representation：Ca1‑xM6(SiO4)2(PO4)2：xEu2+, wherein, M is any one in Mg and Zn, and x is 0.001~0.1.The white light LEDs phosphate blue fluorescent powder has chemical stability and good thermal stability, and raw material production cost cheap and easy to get is low.
Description
Technical field
The present invention relates to rare earth luminescent material technical field, more particularly, to a kind of white light LEDs phosphate blue fluorescent
Powder and preparation method thereof.
Background technology
White light LEDs are a kind of solid electroluminescent devices for converting electrical energy into white light, with energy-conserving and environment-protective, luminous efficiency
Height, small volume, long lifespan, safety, it is easy to use the advantages of, it is considered to be after incandescent lamp, fluorescent lamp, high-voltage gas discharging light it
Forth generation lighting source afterwards, is the green illumination light source of 21 century, is the main product in following illumination market.
At present, realize white light LEDs mainly by following three kinds of modes：(1) blue-light LED chip is combined with yellow fluorescent material；
(2) purple LED chip is combined with fluorescent material with three basic colour；(3) blue-light LED chip is combined with red and green fluorescent material.This three
The method of kind is cheap, preparation technology is simple, and it is that research is also earliest most that wherein blue-light LED chip is combined with yellow fluorescent material
Ripe method, has been realized in commercialization.But up to the present, it still suffers from deficiency, such as colour rendering index is relatively low, colour temperature compared with
It is high, it is impossible to be used as room lighting.In order to improve the colour rendering of white light LEDs, scientists from all over the world have developed blue-ray LED in succession
Chip is combined with red, green fluorescent material and purple LED chip is combined with fluorescent material with three basic colour other two kinds realize white light
LED method.
The launch wavelength of current InGaN chips has moved near ultraviolet region, and higher excitation energy can be provided for fluorescent material
Amount, fluorescent material easily produces visible ray after being stimulated, therefore the species that the fluorescent material based on ultraviolet excitation can be explored is various, has
Good development prospect.In addition, the method combined using purple LED chip with fluorescent material with three basic colour can overcome colour rendering index
The higher deficiency of relatively low, colour temperature, and LED stable luminescent properties, because its color is only determined by fluorescent material.Therefore, using nearly purple
Outer InGaN chips and indigo plant, yellow fluorescent material combine to realize that it is white at present that the scheme of white light has become with three primary colors fluorescent powder
The focus of light LED industry development.Blue colour fluorescent powder is then indispensable composition in the program.
LED is broadly divided into several big systems with blue colour fluorescent powder：Sulphide fluorescent material, silicate fluorescent powder, silicon substrate nitrogen (oxygen)
Compound fluorescent material, phosphate phosphor, aluminate fluorescent powder and other blue colour fluorescent powders.Sulfide blue colour fluorescent powder is such as
CaLaGa3S6O：Eu2+.Silicate blue fluorescent powder is such as：MSiO4：Eu2+(M=Ca, Sr, Ba), Y2SiO5：Ce3+、SrAl2Si2O8：
Eu2+、M3MgSi2O8：Eu2+(M=Ba, Sr) etc..Silicon substrate nitrogen (oxygen) compound blue colour fluorescent powder such as BaSi2O2N2：Eu2+、Ca2Si5N8：
Ce3+And Ba2Si5N8：Ce3+And Sr2Si5N8：Ce3+Deng.Phosphate phosphor such as LiSrPO4：Eu2+、KSrPO4：Eu2+、SrMg2
(PO4)2：Eu2+And Sr5(PO4)3Cl：Eu2+Deng.Aluminate blue fluorescent powder such as BaMgAl10O17：Eu2+.Other blue colour fluorescent powders
Such as Ca2B5O9Cl：Eu2+、SrZnO2：Bi3+And SrZnO2：Bi3+, M+(M=Li, Na, K) etc..
The content of the invention
It is an object of the invention to provide a kind of chemical stability and good thermal stability, the low white light LEDs of production cost are used
Phosphate blue fluorescent powder.It is a further object to provide the preparation of above-mentioned white light LEDs phosphate blue fluorescent powder
Method.
Above-mentioned purpose is realized, the technical solution used in the present invention is：
A kind of white light LEDs phosphate blue fluorescent powder, the fluorescent material has following chemical representation：
Ca1-xM6(SiO4)2(PO4)2：xEu2+, wherein, M is any one in Mg and Zn, and x is 0.001~0.1.
A kind of preparation method of phosphate blue fluorescent powder, comprises the following steps：Compound (1) with calcium carbonate, containing M,
Silica, containing [PO4]3-Compound and europium oxide, by chemical expression Ca1-xM6(SiO4)2(PO4)2：xEu2+Mol ratio claim
The raw material is taken, wherein, M is any one in Mg and Zn, and x is 0.001~0.1, obtains mixture；(2) mixture is filled
Enter crucible, sintered 2~7 hours under the conditions of under reducing atmosphere 1100~1250 DEG C in high temperature furnace, after be cooled to room temperature and obtain
The phosphate blue fluorescent powder.
Preferably, the compound containing M is any one in magnesium carbonate and zinc oxide.
Preferably, PO4]3-Compound is one kind in diammonium hydrogen phosphate or ammonium dihydrogen phosphate.
Preferably, the reducing atmosphere is nitrogen and hydrogen mixture or CO atmosphere.
Using a kind of white light LEDs phosphate blue fluorescent powder of above-mentioned technical proposal, compared with prior art, the present invention
Beneficial effect be：(1) fluorescent material of the invention is good with chemical stability and heat endurance using phosphate as host material
Good, raw material production cost cheap and easy to get is low, the low advantage of sintering temperature.Compared to sulfide blue colour fluorescent powder, the present invention is thermally-stabilised
Property is good.Compared to silicate blue fluorescent powder, grain graininess of the present invention is uniform, and sintering temperature is relatively low.Compared to silicon substrate nitrogen (oxygen) compound
Blue colour fluorescent powder, synthesis technique of the present invention is simple, and sintering temperature is low and raw material is cheap and easy to get.Compared to aluminate blue fluorescent powder,
Preparation temperature of the present invention is low, and grain diameter is smaller, and luminosity and luminous efficiency are high, and physical and chemical performance is stable；(2) this hair
It is bright to compare other phosphate blue fluorescent powders (such as LiSrPO4：Eu2+、KSrPO4：Eu2+), it is to avoid it is empty with decomposition temperature height, exposure
Deliquescent alkali carbonate in gas.
Brief description of the drawings
Fig. 1：Fluorescent powder exciting light spectrogram prepared by the embodiment 1 that the present invention is provided；
Fig. 2：Fluorescent powder launching light spectrogram prepared by the embodiment 1 that the present invention is provided；
Fig. 3：Fluorescent powder XRD spectrum prepared by the embodiment 1 that the present invention is provided.
Embodiment
Embodiment 1
According to Ca0.999Mg6(SiO4)2(PO4)2：0.001Eu2+Weigh CaCO3, MgCO3、SiO2、NH4H2PO4And Eu2O3,
Mol ratio between them is 0.999：6：2：2：0.0005, it is fully ground after being well mixed, places in corundum crucible, place into
In 5%H in high temperature furnace2+ 95%N2Under the nitrogen and hydrogen mixture atmosphere of (volume ratio), it is calcined 7 hours at 1100 DEG C, is subsequently cooled to room
Temperature, obtains phosphate blue fluorescent powder.
Fig. 1 is above-mentioned fluorescent powder exciting light spectrogram, supervisory wavelength 442nm；Fig. 2 is the emission spectrum of above-mentioned fluorescent powder
Figure, excitation wavelength 357nm；Fig. 3 is above-mentioned fluorescent powder XRD spectrum.From figure 1 it appears that the fluorescent material of the present embodiment swashs
Hair spectrum is a wide range, covers ultraviolet and violet region, and excitation peak is located near 357nm, and spectrum peak is high, illustrates the present embodiment
Fluorescent material can effectively be excited by ultraviolet and purple light chip., can be with from Fig. 2 when the excitation wavelength of emission spectrum is 357nm
Find out, the broadband blue light for the being emitted as divalent europium transmitting of the fluorescent material of the present embodiment, emission peak is located near 442nm, illustrates this
The fluorescent material of embodiment is adapted to do ultraviolet and purple light excited blue colour fluorescent powder.From figure 3, it can be seen that the fluorescence of the present embodiment
Powder XRD spectrum shows the d values and relative intensity variation tendency of product, and diffraction maximum relative intensity is higher, has no that raw material and impurity spread out
Peak is penetrated, illustrates that the fluorescence powder purity of the present embodiment synthesis is higher.
Embodiment 2
According to Ca0.95Mg6(SiO4)2(PO4)2：0.05Eu2+Weigh CaCO3, MgCO3、SiO2、NH4H2PO4And Eu2O3, it
Between mol ratio be 0.95：6：2：2：0.025, it is fully ground after being well mixed, places in corundum crucible, place into high temperature
In being calcined 5 hours at 1200 DEG C under CO atmosphere in stove, room temperature is subsequently cooled to, phosphate blue fluorescent powder is obtained.
The fluorescent material PLE of the present embodiment is a wide range, covers ultraviolet and violet region, it is attached that excitation peak is located at 357nm
Closely, spectrum peak is high, illustrates the fluorescent material of the present embodiment and can effectively be excited by ultraviolet and purple light chip.When swashing for emission spectrum
Hair wavelength is 357nm, and the broadband blue light for the being emitted as divalent europium transmitting of the fluorescent material of the present embodiment, emission peak is attached positioned at 442nm
Closely, illustrate that the fluorescent material of the present embodiment is adapted to do ultraviolet and purple light excited blue colour fluorescent powder.The fluorescent material XRD of the present embodiment
The diffraction maximum relative intensity of spectrum is higher, has no raw material and impurity diffraction maximum, illustrates that the fluorescence powder purity of the present embodiment synthesis is higher.
Embodiment 3
According to Ca0.9Mg6(SiO4)2(PO4)2：0.1Eu2+Weigh CaCO3、MgCO3、SiO2、(NH4)2HPO4And Eu2O3, it
Between mol ratio be 0.9：6：2：2：0.05, it is fully ground after being well mixed, places in corundum crucible, place into high temperature furnace
In in 5%H2+ 95%N2Under the nitrogen and hydrogen mixture atmosphere of (volume ratio), it is calcined 2 hours at 1250 DEG C, is subsequently cooled to room temperature, obtains
Phosphate blue fluorescent powder.
The fluorescent material PLE of the present embodiment is a wide range, covers ultraviolet and violet region, it is attached that excitation peak is located at 357nm
Closely, spectrum peak is high, illustrates the fluorescent material of the present embodiment and can effectively be excited by ultraviolet and purple light chip.When swashing for emission spectrum
Hair wavelength is 357nm, and the broadband blue light for the being emitted as divalent europium transmitting of the fluorescent material of the present embodiment, emission peak is attached positioned at 442nm
Closely, illustrate that the fluorescent material of the present embodiment is adapted to do ultraviolet and purple light excited blue colour fluorescent powder.The fluorescent material XRD of the present embodiment
The diffraction maximum relative intensity of spectrum is higher, has no raw material and impurity diffraction maximum, illustrates that the fluorescence powder purity of the present embodiment synthesis is higher.
Embodiment 4
According to Ca0.999Zn6(SiO4)2(PO4)2：0.001Eu2+Weigh CaCO3、ZnO、SiO2、(NH4)2HPO4And Eu2O3,
Mol ratio between them is 0.999：6：2：2：0.0005, it is fully ground after being well mixed, places in corundum crucible, place into
In 5%H in high temperature furnace2+ 95%N2Under the nitrogen and hydrogen mixture atmosphere of (volume ratio), it is calcined 2 hours at 1100 DEG C, is subsequently cooled to room
Temperature, obtains phosphate blue fluorescent powder.
The fluorescent material PLE of the present embodiment is a wide range, covers ultraviolet and violet region, it is attached that excitation peak is located at 357nm
Closely, spectrum peak is high, illustrates the fluorescent material of the present embodiment and can effectively be excited by ultraviolet and purple light chip.When swashing for emission spectrum
Hair wavelength is 357nm, and the broadband blue light for the being emitted as divalent europium transmitting of the fluorescent material of the present embodiment, emission peak is attached positioned at 442nm
Closely, illustrate that the fluorescent material of the present embodiment is adapted to do ultraviolet and purple light excited blue colour fluorescent powder.The fluorescent material XRD of the present embodiment
The diffraction maximum relative intensity of spectrum is higher, has no raw material and impurity diffraction maximum, illustrates that the fluorescence powder purity of the present embodiment synthesis is higher.
Embodiment 5
According to Ca0.9Zn6(SiO4)2(PO4)2：0.1Eu2+Weigh CaCO3、ZnO、SiO2、(NH4)2HPO4And Eu2O3, they
Between mol ratio be 0.9：6：2：2：0.05, it is fully ground after being well mixed, places in corundum crucible, place into high temperature furnace
In being calcined 2 hours at 1250 DEG C under CO atmosphere, room temperature is subsequently cooled to, phosphate blue fluorescent powder is obtained.
The fluorescent material PLE of the present embodiment is a wide range, covers ultraviolet and violet region, it is attached that excitation peak is located at 357nm
Closely, spectrum peak is high, illustrates the fluorescent material of the present embodiment and can effectively be excited by ultraviolet and purple light chip.When swashing for emission spectrum
Hair wavelength is 357nm, and the broadband blue light for the being emitted as divalent europium transmitting of the fluorescent material of the present embodiment, emission peak is attached positioned at 442nm
Closely, illustrate that the fluorescent material of the present embodiment is adapted to do ultraviolet and purple light excited blue colour fluorescent powder.The fluorescent material XRD of the present embodiment
The diffraction maximum relative intensity of spectrum is higher, has no raw material and impurity diffraction maximum, illustrates that the fluorescence powder purity of the present embodiment synthesis is higher.
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, the present invention spirit and
In scope of the claims, any modifications and changes made to the present invention both fall within protection scope of the present invention.
Claims (5)
1. a kind of white light LEDs phosphate blue fluorescent powder, it is characterised in that the fluorescent material has following chemical representation：
Ca1-xM6(SiO4)2(PO4)2：xEu2+, wherein, M is any one in Mg and Zn, and x is 0.001~0.1.
2. a kind of preparation method of phosphate blue fluorescent powder as claimed in claim 1, it is characterised in that comprise the following steps：
(1) compound with calcium carbonate, containing M, silica, containing [PO4]3-Compound and europium oxide, by chemical expression Ca1-xM6
(SiO4)2(PO4)2：xEu2+Mol ratio weigh the raw material, wherein, M be Mg and Zn in any one, x be 0.001~0.1,
Obtain mixture；(2) mixture is loaded into crucible, sintered in high temperature furnace under the conditions of under reducing atmosphere 1100~1250 DEG C
2~7 hours, after be cooled to room temperature and obtain the phosphate blue fluorescent powder.
3. the preparation method of phosphate blue fluorescent powder as claimed in claim 2, it is characterised in that：The compound containing M
For any one in magnesium carbonate and zinc oxide.
4. the preparation method of phosphate blue fluorescent powder as claimed in claim 2, it is characterised in that：It is described to contain [PO4]3-Compound
For one kind in diammonium hydrogen phosphate or ammonium dihydrogen phosphate.
5. the preparation method of phosphate blue fluorescent powder as claimed in claim 2, it is characterised in that：The reducing atmosphere is nitrogen hydrogen
Gaseous mixture or CO atmosphere.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710343597.3A CN107142106A (en) | 2017-05-16 | 2017-05-16 | A kind of blue fluorescent powder for white-light LED and preparation method thereof |
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| CN201710343597.3A CN107142106A (en) | 2017-05-16 | 2017-05-16 | A kind of blue fluorescent powder for white-light LED and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048085A (en) * | 2017-12-12 | 2018-05-18 | 杭州电子科技大学 | A kind of phosphosilicate green emitting phosphor and preparation method thereof |
| CN114590831A (en) * | 2022-03-12 | 2022-06-07 | 陕西师范大学 | LaSi2N3O crystal, fluorescent powder and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029231A (en) * | 2007-01-11 | 2007-09-05 | 复旦大学 | Bivalent-europium-excited base-metal silicate phosphate fluorescent powder and its production |
| CN102492422A (en) * | 2011-12-12 | 2012-06-13 | 苏州大学 | Green emitting phosphor for white-light LEDs and preparation method thereof |
| KR20120072548A (en) * | 2010-12-24 | 2012-07-04 | 한국화학연구원 | Green emitting calcium silicophosphate based phosphor |
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2017
- 2017-05-16 CN CN201710343597.3A patent/CN107142106A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029231A (en) * | 2007-01-11 | 2007-09-05 | 复旦大学 | Bivalent-europium-excited base-metal silicate phosphate fluorescent powder and its production |
| KR20120072548A (en) * | 2010-12-24 | 2012-07-04 | 한국화학연구원 | Green emitting calcium silicophosphate based phosphor |
| CN102492422A (en) * | 2011-12-12 | 2012-06-13 | 苏州大学 | Green emitting phosphor for white-light LEDs and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| SHIRUN YAN等: "Preparation and Properties of Eu2+-Activated Alkaline-Earth Phosphosilicate Phosphors", 《SOLID STATE COMMUNICATIONS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108048085A (en) * | 2017-12-12 | 2018-05-18 | 杭州电子科技大学 | A kind of phosphosilicate green emitting phosphor and preparation method thereof |
| CN108048085B (en) * | 2017-12-12 | 2021-02-02 | 杭州电子科技大学 | Phosphosilicate green fluorescent powder and preparation method thereof |
| CN114590831A (en) * | 2022-03-12 | 2022-06-07 | 陕西师范大学 | LaSi2N3O crystal, fluorescent powder and preparation method |
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Application publication date: 20170908 |