CN105219378B - Silicate blue phosphor for white-light LEDs and preparation method thereof - Google Patents
Silicate blue phosphor for white-light LEDs and preparation method thereof Download PDFInfo
- Publication number
- CN105219378B CN105219378B CN201510627389.7A CN201510627389A CN105219378B CN 105219378 B CN105219378 B CN 105219378B CN 201510627389 A CN201510627389 A CN 201510627389A CN 105219378 B CN105219378 B CN 105219378B
- Authority
- CN
- China
- Prior art keywords
- white
- present
- fluorescent powder
- fluorescent material
- silicate blue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to the technical field of rare earth luminescent materials. Silicate blue phosphor for white-light LEDs has the following chemical formulation: Na2(Ca0.5Sr0.5-x)(SiO4):xEU2+, wherein x ranges from 0.001 to 0.10. The silicate blue phosphor has the advantages that the sintering temperature is low, the synthesis process is simple, and raw materials are low in price and easy to obtain.
Description
Technical field
The present invention relates to rare earth luminescent material technical field, more particularly, to a kind of white light LEDs silicate blue fluorescent
Powder and preparation method thereof.
Background technology
White light LEDs are a kind of solid-state semiconductor devices for converting electrical energy into white light, also known as semiconductor lighting, with efficiency
Many advantages, such as height, small volume, life-span length, safety, low-voltage, energy-saving and environmental protection, by people regard as after incandescent lamp, fluorescent lamp,
Forth generation lighting source after high-voltage gas discharging light, is the main product in following illumination market.
Various white light LEDs preparation methods, wherein blue-light LED chip and yellow fluorescent material group are occurred in that at present
Close, blue-light LED chip with redness and green fluorescent material is combined, purple LED chip combines these three with fluorescent material with three basic colour
Method with price it is low, prepare simply become the main method for preparing white light LEDs.Blue-light LED chip is combined with yellow fluorescent material
It is that to study be also earliest most ripe method, the white light LEDs luminous efficiency of preparation is considerably beyond incandescent lamp, but colour developing refers to
Number is low, and colour temperature is high, it is impossible to use as room lighting.In order to improve the colour rendering of white light LEDs, various countries scientist have developed blue light
LED chip is combined with red, green fluorescent material and purple LED chip combines other two kinds with red, green, blue fluorescent material with three basic colour
The method for realizing white light LEDs.
At present the launch wavelength of InGaN chips has moved near ultraviolet region, can provide higher excitation energy for fluorescent material
Amount, further improves the light intensity of white light LEDs.Because ultraviolet light is invisible, the color of burst of ultraviolel white light LEDs can only be by fluorescent material
Determine, therefore colour stable, colour rendering index is high, using near ultraviolet InGaN chip and indigo plant, Huang fluorescent material or with three primary colours fluorescence
The scheme that powder combines to realize white light becomes the emphasis of current white light LEDs industry development.Blue colour fluorescent powder is can not in the program
The composition for lacking.
LED blue colour fluorescent powders are broadly divided into several big systems：Sulphide fluorescent material, aluminate fluorescent powder, silicate fluorescent
Powder, phosphate phosphor and silicon substrate nitrogen (oxygen) compound fluorescent material.Sulfide blue colour fluorescent powder such as CaLaGa3S6O：Eu2+.Aluminate
Blue colour fluorescent powder such as BaMgAl10O17：Eu2+.Silicate blue fluorescent powder is such as：MSiO4：Eu2+(M=Ca, Sr, Ba), Y2SiO5：
Ce3+、SrAl2Si2O8：Eu2+、M3MgSi2O8：Eu2+(M=Ba, Sr) etc..Phosphate phosphor such as LiSrPO4：Eu2+、KSrPO4：
Eu2+And SrMg2(PO4)2：Eu2+Deng.Silicon substrate nitrogen (oxygen) compound blue colour fluorescent powder such as BaSi2O2N2：Eu2+、Ca2Si5N8：Ce3+With
Ba2Si5N8：Ce3+Deng.
The content of the invention
It is an object of the invention to provide a kind of sintering temperature is low, the simple white light LEDs of synthesis technique are glimmering with silicate blue
Light powder and preparation method thereof.
For achieving the above object, the technical solution used in the present invention is：A kind of white light LEDs silicate blue fluorescent
Powder, with following chemical representation：Na2(Ca0.5Sr0.5-x)(SiO4)：xEu2+, wherein, x is 0.001～0.10.Silicon of the present invention
The preparation method of hydrochlorate blue colour fluorescent powder comprises the steps：By chemical formula Na2(Ca0.5Sr0.5-x)(SiO4)：xEu2+Chemistry
Than weighing corresponding raw material, the raw material is respectively sodium carbonate, calcium carbonate, strontium carbonate, silica and europium oxide for metering, wherein
X is 0.001～0.10；It is ground and obtains mixture；The mixture is loaded into crucible, in high temperature furnace in reducing atmosphere and
Sinter 3～7 hours under the conditions of 1250～1350 DEG C, after be cooled to room temperature and obtain the silicate blue fluorescent powder.
Further, reducing atmosphere of the present invention is nitrogen and hydrogen mixture or CO atmosphere.
Compared with prior art, the invention has the beneficial effects as follows：The fluorescent material of the present invention has with silicate as host material
There are chemical stability and good thermal stability, raw material is inexpensive, be easy to get, the low advantage of sintering temperature.Compare sulfide blue-fluorescence
Powder, heat endurance of the present invention is good.Aluminate blue fluorescent powder is compared, preparation temperature of the present invention is lower than aluminate, and particle compares aluminic acid
Salt is thin, and luminosity is high, luminous efficiency is high and physical and chemical performance is stable.Compare phosphate blue fluorescent powder, particle of the present invention
Epigranular, heat endurance is good.Silicon substrate nitrogen (oxygen) compound blue colour fluorescent powder is compared, sintering temperature of the present invention is low, synthesis technique letter
List and raw material are cheap and easy to get.
Description of the drawings
Fig. 1 be the present invention provide embodiment 1 prepare fluorescent powder exciting light spectrogram, supervisory wavelength 470nm；
Fig. 2 be the present invention provide embodiment 1 prepare fluorescent powder launching light spectrogram, excitation wavelength 380nm；
Fig. 3 is fluorescent powder XRD spectrum prepared by the embodiment 1 that the present invention is provided.
Specific embodiment
Embodiment 1
According to Na2(Ca0.5Sr0.499-x)(SiO4)：0.001Eu2+Weigh Na2CO3、CaCO3、SrCO3、SiO2And Eu2O3, it
Between mol ratio be 1：0.5：0.499：1：0.0005, it is fully ground after being well mixed, in placing corundum crucible, place into
In 1350 DEG C of roastings 7 hours under CO atmosphere in high temperature furnace, after be cooled to room temperature, obtain silicate blue fluorescent powder.
From figure 1 it appears that the fluorescent material PLE of the present embodiment is a wide range, ultraviolet and violet region is covered,
Excitation peak is located near 380nm, is illustrated the fluorescent material of the present embodiment and can effectively be excited by ultraviolet and purple light chip.Work as launching light
The excitation wavelength of spectrum is 380nm, from figure 2 it can be seen that the broadband blue light for being emitted as divalent europium of the fluorescent material of the present embodiment
Transmitting, emission peak is located near 470nm, illustrates that the fluorescent material of the present embodiment is adapted to do ultraviolet and purple light excited blue-fluorescence
Powder.From figure 3, it can be seen that the fluorescent material XRD spectrum of the present embodiment shows the d values and relative intensity variation tendency and mark of product
Accurate Na2(Ca0.5Sr0.499)(SiO4) standard card (ICSD：33941) it is consistent, illustrate the fluorescence powder purity that the present embodiment synthesizes
It is higher.
Embodiment 2
According to Na2(Ca0.5Sr0.499-x)(SiO4)：0.005Eu2+Weigh Na2CO3、CaCO3、SrCO3、SiO2And Eu2O3, it
Between mol ratio be 1：0.5：0.495：1：0.0025, it is fully ground after being well mixed, in placing corundum crucible, then put
Enter in high temperature furnace in 1350 DEG C of roastings 5 hours under CO atmosphere, after be cooled to room temperature, obtain silicate blue fluorescent powder.
The fluorescent material PLE of the present embodiment is a wide range, covers ultraviolet and violet region, and it is attached that excitation peak is located at 380nm
Closely, illustrating the fluorescent material of the present embodiment can effectively be excited by ultraviolet and purple light chip.When the excitation wavelength of emission spectrum is
380nm, the broadband blue light transmitting for being emitted as divalent europium of the fluorescent material of the present embodiment, emission peak is located near 475nm, illustrates this
The fluorescent material of embodiment is adapted to do ultraviolet and purple light excited blue colour fluorescent powder.The fluorescent material XRD spectrum of the present embodiment shows produces
The d values and relative intensity variation tendency of thing and the Na of standard2(Ca0.5Sr0.499)(SiO4) standard card (ICSD：33941) one
Cause, illustrate that the fluorescence powder purity that the present embodiment synthesizes is higher.
Embodiment 3
According to Na2(Ca0.5Sr0.49-x)(SiO4)：0.01Eu2+Weigh Na2CO3、CaCO3、SrCO3、SiO2And Eu2O3, they
Between mol ratio be 1：0.5：0.49：1：0.005, it is fully ground after being well mixed, in placing corundum crucible, place into high temperature
In 1250 DEG C of roastings 7 hours under CO atmosphere in stove, after be cooled to room temperature, obtain silicate blue fluorescent powder.
The fluorescent material PLE of the present embodiment is a wide range, covers ultraviolet and violet region, and it is attached that excitation peak is located at 380nm
Closely, illustrating the fluorescent material of the present embodiment can effectively be excited by ultraviolet and purple light chip.When the excitation wavelength of emission spectrum is
380nm, the broadband blue light transmitting for being emitted as divalent europium of the fluorescent material of the present embodiment, emission peak is located near 477nm, illustrates this
The fluorescent material of embodiment is adapted to do ultraviolet and purple light excited blue colour fluorescent powder.The fluorescent material XRD spectrum of the present embodiment shows produces
The d values and relative intensity variation tendency of thing and the Na of standard2(Ca0.5Sr0.499)(SiO4) standard card (ICSD：33941) one
Cause, illustrate that the fluorescence powder purity that the present embodiment synthesizes is higher.
Embodiment 4
According to Na2(Ca0.5Sr0.45-x)(SiO4)：0.05Eu2+Weigh Na2CO3、CaCO3、SrCO3、SiO2And Eu2O3, it
Between mol ratio be 1：0.5：0.45：1：0.025, it is fully ground after being well mixed, in placing corundum crucible, place into height
In 5%H in warm stove2+ 95%N2In 1300 DEG C of roastings 2 hours under the nitrogen and hydrogen mixture atmosphere of (volume ratio), after be cooled to room temperature, obtain
To silicate blue fluorescent powder.
The fluorescent material PLE of the present embodiment is a wide range, covers ultraviolet and violet region, and it is attached that excitation peak is located at 380nm
Closely, illustrating the fluorescent material of the present embodiment can effectively be excited by ultraviolet and purple light chip.When the excitation wavelength of emission spectrum is
380nm, the broadband blue light transmitting for being emitted as divalent europium of the fluorescent material of the present embodiment, emission peak is located near 480nm, illustrates this
The fluorescent material of embodiment is adapted to do ultraviolet and purple light excited blue colour fluorescent powder.The fluorescent material XRD spectrum of the present embodiment shows produces
The d values and relative intensity variation tendency of thing and the Na of standard2(Ca0.5Sr0.499)(SiO4) standard card (ICSD：33941) one
Cause, illustrate that the fluorescence powder purity that the present embodiment synthesizes is higher.
Embodiment 5
According to Na2(Ca0.5Sr0.4)(SiO4)：0.1Eu2+Weigh Na2CO3、CaCO3、SrCO3、SiO2And Eu2O3, they it
Between mol ratio be 1：0.5：0.4：1：0.05, it is fully ground after being well mixed, in placing corundum crucible, in placing into high temperature furnace
In 5%H2+ 95%N2In 1250 DEG C of roastings 3 hours under the nitrogen and hydrogen mixture atmosphere of (volume ratio), after be cooled to room temperature, obtain silicic acid
Salt blue colour fluorescent powder.
The fluorescent material PLE of the present embodiment is a wide range, covers ultraviolet and violet region, and it is attached that excitation peak is located at 380nm
Closely, illustrating the fluorescent material of the present embodiment can effectively be excited by ultraviolet and purple light chip.When the excitation wavelength of emission spectrum is
380nm, the broadband blue light transmitting for being emitted as divalent europium of the fluorescent material of the present embodiment, emission peak is located near 483nm, illustrates this
The fluorescent material of embodiment is adapted to do ultraviolet and purple light excited blue colour fluorescent powder.The fluorescent material XRD spectrum of the present embodiment shows produces
The d values and relative intensity variation tendency of thing and the Na of standard2(Ca0.5Sr0.499)(SiO4) standard card (ICSD：33941) one
Cause, illustrate that the fluorescence powder purity that the present embodiment synthesizes is higher.
Claims (3)
1. a kind of silicate blue fluorescent powder for white-light LED, it is characterised in that the fluorescent material has following chemical representation：Na2
(Ca0.5Sr0.5-x)(SiO4)：xEu2+, wherein, x is 0.001～0.10.
2. the preparation method of the silicate blue fluorescent powder for white-light LED described in a kind of claim 1, it is characterised in that include as
Lower step：By chemical formula Na2(Ca0.5Sr0.5-x)(SiO4)：xEu2+Stoichiometric proportion weigh corresponding raw material, the raw material point
Not Wei sodium carbonate, calcium carbonate, strontium carbonate, silica and europium oxide；It is ground and obtains mixture；The mixture is loaded into earthenware
Crucible, sinters 3～7 hours in high temperature furnace under the conditions of reducing atmosphere and 1250～1350 DEG C, after be cooled to room temperature and obtain described
Silicate blue fluorescent powder.
3. the preparation method of silicate blue fluorescent powder for white-light LED as claimed in claim 2, it is characterised in that：It is described to go back
Primordial Qi atmosphere is CO atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510627389.7A CN105219378B (en) | 2015-09-28 | 2015-09-28 | Silicate blue phosphor for white-light LEDs and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510627389.7A CN105219378B (en) | 2015-09-28 | 2015-09-28 | Silicate blue phosphor for white-light LEDs and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105219378A CN105219378A (en) | 2016-01-06 |
| CN105219378B true CN105219378B (en) | 2017-04-26 |
Family
ID=54988663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510627389.7A Active CN105219378B (en) | 2015-09-28 | 2015-09-28 | Silicate blue phosphor for white-light LEDs and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105219378B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116120922B (en) * | 2023-02-17 | 2024-01-30 | 山东大学 | Eu (Eu) 2+ Silicate doped fluorescent material and preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100580052C (en) * | 2005-06-14 | 2010-01-13 | 大连路明发光科技股份有限公司 | Red light-emitting phosphor powder excited by UV and blue light LED |
| US7662311B2 (en) * | 2005-09-06 | 2010-02-16 | Niigata University | Fluorescent substance for light-emitting diode |
| CN103059838B (en) * | 2012-10-31 | 2014-07-16 | 苏州大学 | Eu<2+> activated silicate yellow fluorescent powder as well as preparation method and application thereof |
-
2015
- 2015-09-28 CN CN201510627389.7A patent/CN105219378B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105219378A (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104726101B (en) | White light LEDs single-substrate white launches fluorophosphate fluorescent material and preparation method | |
| CN104927865A (en) | Halophosphate blue phosphor powder for white light LED and preparation method of halophosphate blue phosphor powder | |
| CN111154488A (en) | Terbium-doped germanate green fluorescent powder for white light LED and preparation method thereof | |
| CN101597493A (en) | A kind of alkaline-earth metal silicophosphate fluorescent material and manufacture method and application | |
| CN102260498A (en) | Nitric oxide orange red fluorescent powder for white LED (light-emitting diode) and preparation method thereof | |
| CN102585812B (en) | Dark red fluorescent powder and preparation method thereof | |
| CN104498031B (en) | A kind of phosphate yellow fluorescent powder and preparation method thereof for white light LEDs | |
| CN110129050A (en) | It is a kind of singly to mix single-phase full spectrum fluorescent powder and preparation method | |
| CN107129805B (en) | Europium ion doped silicate white light fluorescent powder and preparation method thereof | |
| CN107987828A (en) | A kind of mayenite structure fluorescent powder of LED white light emissions | |
| CN110240900B (en) | Eu (Eu)2+Doped narrow-band green luminescent material, preparation method and illumination and display light source | |
| CN105778904B (en) | A kind of gallium aluminium hydrochlorate base fluorescent material and preparation method thereof | |
| CN104531144A (en) | CaMg<2>Al<16>O<27>:Mn <4+> red fluorescent powder and preparation technology thereof | |
| CN107541211B (en) | Blue light-emitting fluorescent powder suitable for near ultraviolet light excitation and preparation method and application thereof | |
| CN108034423B (en) | Mn (manganese)2+Ion-doped silicate red fluorescent powder, preparation method and application | |
| CN105219378B (en) | Silicate blue phosphor for white-light LEDs and preparation method thereof | |
| CN108264897B (en) | Phosphor and light emitting device having the same | |
| CN107142106A (en) | A kind of blue fluorescent powder for white-light LED and preparation method thereof | |
| Hur et al. | Enhancement of fluorescence by Ce3+ doping in green-emitting Ca15 (PO4) 2 (SiO4) 6: Eu2+ phosphor for UV-based w-LEDs | |
| CN106905967A (en) | A kind of borophosphate green emitting phosphor and preparation method thereof | |
| CN104804742B (en) | Red fluorescent powder for white light LED and preparation method thereof | |
| CN104327852A (en) | Silicon/germinate phosphor, preparation method and application thereof | |
| CN106867534A (en) | A kind of white light LEDs borate red fluorescent powder and preparation method thereof | |
| CN108587621A (en) | A kind of ultraviolet or near ultraviolet excitated white light LEDs Color tunable silicate fluorescent powder and preparation method thereof | |
| CN108048085B (en) | Phosphosilicate green fluorescent powder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |