CN109957401A - A kind of ultraviolet LED single-phase warm white fluorescent powder and preparation method - Google Patents
A kind of ultraviolet LED single-phase warm white fluorescent powder and preparation method Download PDFInfo
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- CN109957401A CN109957401A CN201810523714.9A CN201810523714A CN109957401A CN 109957401 A CN109957401 A CN 109957401A CN 201810523714 A CN201810523714 A CN 201810523714A CN 109957401 A CN109957401 A CN 109957401A
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- fluorescent powder
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- ultraviolet led
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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 invention discloses a kind of ultraviolet LED single-phase warm white fluorescent powder and preparation method, Mg2+The whitlockite type Ca of doping vario-property10.5‑x‑yMgx(PO4)7:yEu2+(0≤x≤1.50) single-phase fluorescent powder realizes the continuous transmitting of covering visible light spectrum under the excitation of ultraviolet light, compensates for the shortcomings that commercial fluorescence lacks red emission.The present invention provides a kind of new single-phase fluorescent powder for the preparation of high color rendering index (CRI) warm white LED, will can be obtained high color rendering index (CRI) warm white LED in 365nm ultraviolet chip with simple single-phase fluorescent powder packaging.The Mg2+The single-phase fluorescent powder colour rendering index of doping vario-property is high, and preparation method is simple, low in cost, has good industrial prospect.
Description
Technical field
The present invention relates to technical field of LED illumination more particularly to a kind of ultraviolet LED single-phase warm white fluorescent powder and preparations
Method.
Background technique
White light LEDs (light emitting diode) are expected to become the existing fluorescent lamp of forth generation artificial light sources substitution,
Realize conversion of the electric energy to luminous energy higher efficiency.The implementation of existing white light LEDs generally there are several types of: (1) it is blue, green,
The LED chip of red three primary colours color assembles to obtain white light, and this mode is not only with high costs but also can be because the color of three kinds of chips declines
Rate difference leads to serious color difference；(2) blue chip and yellow (or green and red) phosphor combination, this mode by
In business yellow fluorescent powder Y3Al5O12:Ce3+(YAG:Ce) there is a serious shortage of feux rouges will lead to lower colour rendering index and higher color
Temperature；(3) ultraviolet chip and blue, green, red trichromatism phosphor combination, color difference caused by this combination can overcome blue chip color to decline with
Lack the feux rouges disadvantages such as cause colour rendering index low.But the shortcomings that being reabsorbed there is also energy between different fluorescent powders.Therefore, it develops
It is a kind of energy between different fluorescent powders to be overcome very well to inhale again in the single-phase fluorescent powder under burst of ultraviolel with full spectral emissions
The shortcomings that receipts.
Currently, realizing the full spectral emissions or an arduous challenge of single activator ion in single-phase matrix.Phosphorus
Calcium mine type β-Ca3(PO4)2With cationic site abundant and there is numerous derivative structures, is very suitable to mixing for rare earth ion
It is miscellaneous, especially Eu2+And Ce3+.Because of Eu2+And Ce3+F-d transition it is closely related with the Local Structure of host material, in β-Ca3
(PO4)2The Local Structure of modulation matrix can be adulterated in structure by different ions to regulate and control Eu2+Or Ce3+Fluorescence.Ion
The variation of Local Structure caused by adulterating is Eu2+Coordination environment abundant is provided, is the Eu of different local environments2+It generates different
The transmitting of color creates advantage.
It is published in the recent period with the most similar technology of the present invention entitled on Chem.Eng.J.2017,326,667-679
《Controlling multi luminescent centers via anionic polyhedron substitution to
achieve single Eu2+activated high-color-rendering white light/tunable
emissions in single-phased Ca2(BO3)1-x(PO4)xCl phosphors for ultraviolet
Converted LEDs " paper, it was recently reported that use PO4 3-Anion substitutes BO3 3-Anion realizes Eu2+It is white in single-phase matrix
Light emitting.This method PO4Tetrahedron substitutes BO3Plane triangle is not only easy to produce miscellaneous phase, but also Eu2+Transmitting can not
Entire visible region is covered, especially in the transmitting wretched insufficiency of red light district 620-770nm.As a result lead to the LED colour developing of assembling
Index is relatively low, especially R9Value only 39 or so, this severely limits application of this technology in terms of solid state lighting.
Based on discussed above, we have developed a kind of strategies of completely new cation substitution: in β-Ca3(PO4)2In structure
Mix that radius is smaller, the higher Mg of electronegativity2+Ion, Eu2+The occupy-place of ion is in Mg2+It is migrated under the guiding of ion, as a result
Lead to multiple Eu2+The emission spectrum of fluorescence centre can cover entire visible region.This method is regulation Eu2+Luminosity, it is special
It is not by modulation Eu2+The occupancy of ion regulates and controls Eu2+Luminescent behavior provide completely new thinking.
Summary of the invention
The object of the invention is that providing a kind of ultraviolet LED single-phase warm white fluorescent powder to solve the above-mentioned problems
And preparation method.
The present invention through the following technical solutions to achieve the above objectives:
A kind of single-phase warm white fluorescent powder of ultraviolet LED of the invention, the chemical composition of the fluorescent powder are Ca10.5-x-yMgx
(PO4)7:yEu2+, wherein 0≤x≤1.50,0 < y≤0.08.
A kind of preparation method of the single-phase warm white fluorescent powder of ultraviolet LED of the present invention, comprising the following steps:
Step 1: being the CaCO of (10.5-x-y): x:7:(y/2) ratio by the ratio between amount of substance of Ca:Mg:P:Eu3、
MgO、NH4H2PO4、Eu2O3For raw material ground and mixed uniformly after tabletting, with the heating rate of 3 DEG C/min at 600 DEG C pre-burning 4h；
Step 2: the solid after pre-burning is regrind and is uniformly mixed, is pressed into diameter 20mm later, thickness is about 1mm
Thin slice, with the heating rate of 8 DEG C/min in 10%H21000-1200 DEG C of calcining 8h in the reducing atmosphere of -90%Ar；
Step 3: after waiting samples to be cooled to room temperature, taking-up is fully ground to obtain Mg2+The whitlockite type of doping vario-property
Ca10.5-x-yMgx(PO4)7:yEu2+(0≤x≤1.50) single-phase fluorescent powder.
Preferably, the calcined temperature in step 1 is 600 DEG C, burn-in time 4h.
Preferably, the calcination temperature in step 2 is 1000-1200 DEG C, calcination time 8h, and calcination atmosphere is mixed for argon hydrogen
Close gas.
A kind of purposes of the fluorescent powder, by the Ca9.69Mg0.75(PO4)7:0.06Eu2+White fluorescent powder encapsulation
It can get warm white (R on 365nm chipa=85, R9=91).
The specific excites scope of single-phase fluorescent powder of the invention is 250-450nm, transmitting range 380-820nm.
The beneficial effects of the present invention are:
The present invention is a kind of ultraviolet LED single-phase warm white fluorescent powder and preparation method, compared with prior art, the present invention
Phosphor host be Mg2+β-the Ca of doping3(PO4)2, low in raw material price；The high temperature solid-state method is suitble to extensive
Production, is advantageously implemented commercialization.Fluorescent powder preparation condition of the invention is mild, and colour rendering index with higher, has
Higher industrial prospect.
Detailed description of the invention
Fig. 1 obtains the XRD diagram of sample when being x >=1.50 in embodiment 1；
Fig. 2 obtains the XRD diagram of sample when being x≤1.50 in embodiment 1；
Fig. 3 is Ca in embodiment 48.94Mg1.5(PO4)7:0.06Eu2+Exciting light of the fluorescent powder under 630 and 418nm monitoring
Spectrum；
Fig. 4 is Ca10.44-xMgx(PO4)7:0.06Eu2+Transmitting of (wherein 0≤x≤1.50) fluorescent powder under 365nm excitation
Spectrum and the photo in kind under 365nm ultraviolet lamp；
Fig. 5 is Ca10.44-xMgx(PO4)7:0.06Eu2+Transmitting of (wherein 0≤x≤1.50) fluorescent powder under 340nm excitation
Spectrum；
Fig. 6 is Ca in embodiment 58.94Mg1.5(PO4)7:0.06Eu2+Emission spectrum and material object under different excitation wavelengths
Photo；
Fig. 7 is Ca in embodiment 510.44-xMgx(PO4)7:0.06Eu2+(wherein x=0.75,1.00,1.25 and 1.50) is glimmering
Light powder is encapsulated in electroluminescent spectrogram and photo in kind in 365nm ultraviolet chip；
Fig. 8 is Ca10.44-xMgx(PO4)7:0.06Eu2+The CIE of (wherein x=0.75,1.00,1.25 and 1.50) fluorescent powder
Chromaticity coordinates figure.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings:
It is as shown in Figures 1 to 8: a kind of single-phase warm white fluorescent powder of ultraviolet LED of the invention, the chemical composition of the fluorescent powder
For Ca10.5-x-yMgx(PO4)7:yEu2+, wherein 0≤x≤1.50,0 < y≤0.08.
A kind of preparation method of the single-phase warm white fluorescent powder of ultraviolet LED of the present invention, comprising the following steps:
Step 1: being the CaCO of (10.5-x-y): x:7:(y/2) ratio by the ratio between amount of substance of Ca:Mg:P:Eu3、
MgO、NH4H2PO4、Eu2O3For raw material ground and mixed uniformly after tabletting, with the heating rate of 3 DEG C/min at 600 DEG C pre-burning 4h；
Step 2: the solid after pre-burning is regrind and is uniformly mixed, is pressed into diameter 20mm later, thickness is about 1mm
Thin slice, with the heating rate of 8 DEG C/min in 10%H21000-1200 DEG C of calcining 8h in the reducing atmosphere of -90%Ar；
Step 3: after waiting samples to be cooled to room temperature, taking-up is fully ground to obtain Mg2+The whitlockite type of doping vario-property
Ca10.5-x-yMgx(PO4)7:yEu2+(0≤x≤1.50) single-phase fluorescent powder.
Preferably, the calcined temperature in step 1 is 600 DEG C, burn-in time 4h.
Preferably, the calcination temperature in step 2 is 1000-1200 DEG C, calcination time 8h, and calcination atmosphere is mixed for argon hydrogen
Close gas.
A kind of purposes of the fluorescent powder, by the Ca9.69Mg0.75(PO4)7:0.06Eu2+White fluorescent powder encapsulation
It can get warm white (R on 365nm chipa=85, R9=91).
The specific excites scope of single-phase fluorescent powder of the invention is 250-450nm, transmitting range 380-820nm.
Embodiment 1
The chemical formula of single-phase warm white LED fluorescent powder of the invention is Ca10.5-x-yMgx(PO4)7:yEu2+, wherein 0≤x
≤ 1.50,0 < y≤0.08.And x value may not exceed 1.50, otherwise there is miscellaneous phase generation.
Embodiment 2
The present invention uses high temperature solid-state method, with the CaCO of stoichiometric ratio3、MgO、NH4H2PO4、Eu2O3For raw material, raw material
It is that analysis is pure.First 600 DEG C of pre-burning 4h in air, regrinding is pressed into diameter 20mm after being uniformly mixed, thickness is about 1mm
Thin slice, in 10%H21000-1200 DEG C of calcining 8h in the reducing atmosphere of -90%Ar.And it is cooled to room in a reducing atmosphere
Wen Hou obtains finished product fluorescent powder after being fully ground.
Embodiment 3
Calcination temperature is 1000-1200 DEG C.Fluorescent powder Ca lower to Mg content10.5-x-yMgx(PO4)7:yEu2+, (wherein
0≤x < 0.75,0 < y≤0.08), calcination temperature preferentially selects 1000 DEG C.Fluorescent powder Ca higher to Mg content10.5-x-yMgx
(PO4)7:yEu2+, (wherein 0.75≤x≤1.50,0 < y≤0.08), calcination temperature preferentially selects 1200 DEG C.Suitable Mg doping
β-Ca can be improved3(PO4)2The stability of structure, the higher fluorescent powder Ca of Mg content10.5-x-yMgx(PO4)7:yEu2+, (wherein
0.75≤x≤1.50,0 < y≤0.08) 1200 DEG C are increased in calcination temperature will not generate miscellaneous phase.
Embodiment 4
So that the relative intensity of broadband emission of the fluorescent powder at 480-820nm enhances, fluorescent powder shines for the doping of Mg
Color is from the bluish violet of original sample by white light area to magenta gradually transition.In addition, the exciting light of the doping fluorescent powder with Mg
Spectrum broadens, and extinction cutoff wavelength extends to 450nm from the 370nm of original sample.
Embodiment 5
It will be fully ground after sintering in powdered fluorescent powder, fluorescent powder/silica gel=1/2 ratio mixing in mass ratio is equal
Even post package obtains the warm white LED of UV excitation in the ultraviolet chip of 365nm after natural drying.Due to gained fluorescent powder
The intensity of emission peak changes with the variation of excitation wavelength at 418nm and 630nm two, causes the luminescent color of fluorescent powder also with sharp
It sends out the variation of wavelength and changes.The cost of luminous intensity and UV LED chip is taken into account, preferentially selects 365nm ultraviolet LED core here
Piece.The wave-length coverage of LED chip can not limit the scope of the invention.
Embodiment 6
LED light parameter in embodiment 4 is as follows
Wherein Ca9.69Mg0.75(PO4)7:0.06Eu2+The LED-1 of encapsulation shows warm white light emitting, and colour rendering index RaIt is high
Up to 85, especially R9Value up to 91.This illustrates that fluorescent powder of the invention has well in terms of the solid state lighting of high quality is shown
Commercial prospect.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (4)
1. a kind of single-phase warm white fluorescent powder of ultraviolet LED, it is characterised in that: the chemical composition of the fluorescent powder is Ca10.5-x-yMgx
(PO4)7:yEu2+, wherein 0≤x≤1.50,0 < y≤0.08.
2. a kind of ultraviolet LED preparation method of single-phase warm white fluorescent powder, which comprises the following steps:
Step 1: being the CaCO of (10.5-x-y): x:7:(y/2) ratio by the ratio between amount of substance of Ca:Mg:P:Eu3、MgO、
NH4H2PO4、Eu2O3For raw material ground and mixed uniformly after tabletting, with the heating rate of 3 DEG C/min at 600 DEG C pre-burning 4h；
Step 2: the solid after pre-burning is regrind and is uniformly mixed, is pressed into diameter 20mm later, thickness is about the thin of 1mm
Piece, with the heating rate of 8 DEG C/min in 10%H21000-1200 DEG C of calcining 8h in the reducing atmosphere of -90%Ar；
Step 3: after waiting samples to be cooled to room temperature, taking-up is fully ground to obtain Mg2+The whitlockite type Ca of doping vario-property10.5-x-yMgx
(PO4)7:yEu2+(0≤x≤1.50) single-phase fluorescent powder.
3. the ultraviolet LED according to claim 2 preparation method of single-phase warm white fluorescent powder, it is characterised in that: step
Calcined temperature in one is 600 DEG C, burn-in time 4h.
4. the ultraviolet LED according to claim 2 preparation method of single-phase warm white fluorescent powder, it is characterised in that: step
Calcination temperature in two is 1000-1200 DEG C, and calcination time 8h, calcination atmosphere is argon hydrogen mixture.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111778021A (en) * | 2020-07-14 | 2020-10-16 | 新疆师范大学 | High-luminescence thermal-stability bluish violet luminescent material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756676A (en) * | 2014-01-07 | 2014-04-30 | 杭州电子科技大学 | Ultraviolet excited phosphate fluorescent powder with adjustable emission wavelength |
| CN107189779A (en) * | 2017-06-02 | 2017-09-22 | 中国计量大学 | A kind of white light LEDs adjustable phosphate phosphor of spectrum and preparation method thereof |
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2018
- 2018-05-28 CN CN201810523714.9A patent/CN109957401A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756676A (en) * | 2014-01-07 | 2014-04-30 | 杭州电子科技大学 | Ultraviolet excited phosphate fluorescent powder with adjustable emission wavelength |
| CN107189779A (en) * | 2017-06-02 | 2017-09-22 | 中国计量大学 | A kind of white light LEDs adjustable phosphate phosphor of spectrum and preparation method thereof |
Non-Patent Citations (3)
| Title |
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| WENLI ZHOU ET AL.: "Synthesis and photoluminescence properties of a cyan-emitting phosphor Ca3(PO4)2:Eu2+ for white light-emitting diodes", 《OPTICAL MATERIALS》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111778021A (en) * | 2020-07-14 | 2020-10-16 | 新疆师范大学 | High-luminescence thermal-stability bluish violet luminescent material and preparation method and application thereof |
| CN111778021B (en) * | 2020-07-14 | 2022-11-04 | 新疆师范大学 | High-luminescence thermal-stability bluish violet luminescent material and preparation method and application thereof |
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