CN102277166A - Europium ion and manganese ion-codoped magnesium aluminum phosphate fluorescent powder and preparation method thereof - Google Patents

Europium ion and manganese ion-codoped magnesium aluminum phosphate fluorescent powder and preparation method thereof Download PDF

Info

Publication number
CN102277166A
CN102277166A CN201110246959XA CN201110246959A CN102277166A CN 102277166 A CN102277166 A CN 102277166A CN 201110246959X A CN201110246959X A CN 201110246959XA CN 201110246959 A CN201110246959 A CN 201110246959A CN 102277166 A CN102277166 A CN 102277166A
Authority
CN
China
Prior art keywords
ion
fluorescent material
codoped
phosphoric acid
preparation
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.)
Pending
Application number
CN201110246959XA
Other languages
Chinese (zh)
Inventor
邱建备
宋志国
徐圆圆
杨正文
周大成
尹兆益
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunming University of Science and Technology
Original Assignee
Kunming University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kunming University of Science and Technology filed Critical Kunming University of Science and Technology
Priority to CN201110246959XA priority Critical patent/CN102277166A/en
Publication of CN102277166A publication Critical patent/CN102277166A/en
Pending legal-status Critical Current

Links

Images

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 provides europium ion and manganese ion-codoped magnesium aluminum phosphate fluorescent powder and a preparation method thereof. The fluorescent powder comprises a component with a chemical composition formula of Mg1-x-yEuxMnyAl(PO4)zO, wherein x is equal to 0.001 to 0.1, y is equal to 0.001 to 0.1, and z is equal to 0.9 to 1.2. The fluorescent powder can be excited effectively by ultraviolet light and blue light to emit broadband visible fluorescent light of which the wavelength range is from 400 to 700 nanometers and the central peak is positioned in a place of about 450 nanometers and 640 nanometers. The full-color white light fluorescent powder can be matched with a near ultraviolet tube core light emitting diode (LED), and is used for white light LEDs or energy-saving lamps.

Description

Phosphoric acid magnalium fluorescent material of europium ion and mn ion codoped and preparation method thereof
Technical field
The present invention relates to illumination and show the fluorescent material technology, be specifically related to phosphoric acid magnalium fluorescent material of a kind of europium ion and mn ion codoped and preparation method thereof, belong to the fluorescent material technical field.
Background technology
Energy-conserving and environment-protective have been the main flows of Future Social Development.Compare with electricity-saving lamp with the incandescent light of present widespread use, based on LED(Light Emitting Diode) solid-state lighting lamp the advantage of all many-sides such as energy-conservation, stable, environmental protection is arranged.Therefore develop semiconductor lighting and help the environmental problem that exists in final result energy dilemma and original incandescent light and the electricity-saving lamp.In order to realize white light LEDs, a kind of reasonable method is to utilize the light conversion phosphor.It is that generation is white luminous that present common white light LEDs mainly is to use the YAG:Ce fluorescent material of GaN base blue LED collocation emission sodium yellow.Because white light is to be formed by the yellow fluorescence of fluorescent material and the blue light of LED, the glow color of device changes with the variation of driving voltage and fluorescent coating thickness, and color reducibility is poor, and colour rendering index is low.For addressing the above problem, adopt near-ultraviolet light (380～410 n m) In GaN tube core to excite three primary colors fluorescent powder to realize that white light LEDs has become at present one of focus of these field research and development in the world.Because vision is to the insensitivity of near-ultraviolet light, the color of this class white light LEDs is only by the fluorescent material decision, therefore, colour stable, color reducibility and colour rendering index height are considered to the leading of White-light LED illumination of new generation.
At present, the white emitting fluorescent powder that is complementary with the near-ultraviolet light tube core lacks, and luminescent properties is undesirable, and this white emitting fluorescent powder generally adopts the way of mixing three kinds of primary colours fluorescent material of red, green, blue to make.Because exist color to absorb and proportioning regulation and control problem between the mixture, luminous efficiency and color rendition performance are a greater impact, and therefore, develop panchromatic single white emitting fluorescent powder and have crucial meaning again.But the near ultraviolet white light LED fluorescent powder kind of using is few at present, and mainly is that high pressure is this series phosphor powder preparation temperature height of fluorescent material of silicate series, and the high temperature optical attenuation is apparent in view simultaneously, can't satisfy the needs of white-light illuminating with ultraviolet LED.Therefore develop near ultraviolet LED fluorescent material, reduce the kind and the ratio of fluorescent material collocation, can effectively reduce mixing uniformity and colour temperature drifting problem with wide spectral emissions.By contrast, it is good also to lack excellent performance, thermostability and chemical stability in the market, colour gamut broad, the wide spectrum fluorescent material that can be excited by near ultraviolet LED.
Summary of the invention
The objective of the invention is at existing near ultraviolet LED illumination fluorescent material colour gamut narrow, need multiple fluorescent material compound, the deficiency of preparation method's cost height, complexity provides phosphoric acid magnalium fluorescent material of a kind of europium ion and mn ion codoped and preparation method thereof, realizes by following technical proposal.
The phosphoric acid magnalium fluorescent material of a kind of europium ion and mn ion codoped comprises that chemical constitution formula is Mg 1-x-yEu xMn yAl (PO 4) zThe component of O, wherein, x=0.001～0.1, y=0.001～0.1, z=0.9～1.2.
Another object of the present invention is to provide the preparation method of the phosphoric acid magnalium fluorescent material of a kind of europium ion and mn ion codoped, through following each step:
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.8～0.998 ︰, 0.001～0.1 ︰, 0.001～0.1 ︰ 0.9～1.2, gets magnesium-containing compound, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) step (1) gained compound is warming up to 1000～1400 ℃, is incubated 0.5～4 hour, again naturally cooling;
(3) with step (2) gained compound, place CO or H 2+ N 2Under the environment of reducing gas, under 800 ~ 1300 ℃, be incubated 0.5～2 hour, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 1-x-yEu xMn yAl (PO 4) zThe phosphoric acid magnalium fluorescent material of the europium ion of O and mn ion codoped.
The preparation method of the phosphoric acid magnalium fluorescent material of a kind of europium ion and mn ion codoped, also can pass through following each step:
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.8～0.998 ︰, 0.001～0.1 ︰, 0.001～0.1 ︰ 0.9～1.2, gets magnesium-containing compound, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) with step (1) gained compound, place CO or H 2+ N 2Under the environment of reducing gas, be warming up to 1000～1400 ℃, be incubated 0.5～4 hour, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 1-x-yEu xMn yAl (PO 4) zThe phosphoric acid magnalium fluorescent material of the europium ion of O and mn ion codoped.
Described magnesium-containing compound is MgO, MgCO 3, Mg (HCO 3) OH, Mg (OH) 2In one or several.
The present invention compares with existing near ultraviolet LED excited fluorescent powder material, have following outstanding advantage: phosphoric acid magnalium fluorescent material near-ultraviolet light provided by the invention has efficient response characteristic, under near ultraviolet excitation, can realize wavelength region 400 nm to 700 nm, central peak is positioned at the broadband visible fluorescence about 450 nm and 640 nm, is expected to become the illumination fluorescent material that near ultraviolet LED excites.The chemical stability of this fluorescent material is good, and the preparation desired raw material is few, and the preparation method is simple, can effectively reduce cost; Better with near ultraviolet LED chip coupling, visible light luminous intensity height, luminous wide waveband under near ultraviolet excitation, color developing is better, can reduce other face and penetrate the fluorescent material collocation.
Description of drawings:
Fig. 1 is the europium ion of embodiment 1 preparation and the phosphoric acid magnalium fluorescent material Mg of mn ion codoped 1-x-yEu xMn yAl (PO 4) zO(x=0.005; Y=0.005; Z=1) at the exciting light spectrogram at 450 nm places;
Fig. 2 is the europium ion of embodiment 1 preparation and the phosphoric acid magnalium fluorescent material Mg of mn ion codoped 1-x-yEu xMn yAl (PO 4) zO(x=0.005; Y=0.005; Z=1) X-ray diffractogram; Wherein, a is the standard card spectral line, and b is the sample spectrogram of example 1 preparation;
Fig. 3 is the europium ion of embodiment 1 preparation and the phosphoric acid magnalium fluorescent material Mg of mn ion codoped 1-x-yEu xMn yAl (PO 4) zO(x=0.005; Y=0.005; Z=1) the emmission spectrum figure under 365 nm excite.
Embodiment
Further illustrate content of the present invention below in conjunction with embodiment, but these examples do not limit protection scope of the present invention.
Embodiment 1
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.99 ︰, 0.005 ︰, 0.005 ︰ 1, gets MgO, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) step (1) gained compound is warming up to 1400 ℃, is incubated 0.5 hour, again naturally cooling;
(3) with step (2) gained compound, place under the environment of CO reducing gas, under 1300 ℃, be incubated 0.5 hour, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 0.99Eu 0.005Mn 0.005Al (PO 4) europium ion of O and the phosphoric acid magnalium fluorescent material of mn ion codoped.
Embodiment 2
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.897 ︰, 0.003 ︰, 0.1 ︰ 1, gets MgCO 3, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) step (1) gained compound is warming up to 1300 ℃, is incubated 2 hours, again naturally cooling;
(3) with step (2) gained compound, place H 2+ N 2Under the environment of reducing gas, under 1200 ℃, be incubated 1 hour, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 0.897Eu 0.003Mn 0.1Al (PO 4) europium ion of O and the phosphoric acid magnalium fluorescent material of mn ion codoped.
Embodiment 3
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.898 ︰, 0.1 ︰, 0.002 ︰ 0.9, gets Mg (HCO 3) OH, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) with step (1) gained compound, place H 2+ N 2Under the environment of reducing gas, be warming up to 1300 ℃, be incubated 2 hours, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 0.898Eu 0.1Mn 0.002Al (PO 4) 0.9The phosphoric acid magnalium fluorescent material of the europium ion of O and mn ion codoped.
Embodiment 4
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.8 ︰, 0.1 ︰, 0.1 ︰ 1.2, gets Mg (OH) 2, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) with step (1) gained compound, place under the environment of CO reducing gas, be warming up to 1000 ℃, be incubated 4 hours, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 0.8Eu 0.1Mn 0.1Al (PO 4) 1.2The phosphoric acid magnalium fluorescent material of the europium ion of O and mn ion codoped.
Embodiment 5
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.998 ︰, 0.001 ︰, 0.001 ︰ 1.2, gets Mg (HCO 3) OH, Mg (OH) 2, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) step (1) gained compound is warming up to 1000 ℃, is incubated 4 hours, again naturally cooling;
(3) with step (2) gained compound, place under the environment of CO reducing gas, under 800 ℃, be incubated 2 hours, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 0.998Eu 0.001Mn 0.001Al (PO 4) 1.2The phosphoric acid magnalium fluorescent material of the europium ion of O and mn ion codoped.
Embodiment 6
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.998 ︰, 0.001 ︰, 0.001 ︰ 1, gets MgO, MgCO 3, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) with step (1) gained compound, place H 2+ N 2Under the environment of reducing gas, be warming up to 1400 ℃, be incubated 0.5 hour, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 0.998Eu 0.001Mn 0.001Al (PO 4) europium ion of O and the phosphoric acid magnalium fluorescent material of mn ion codoped.
Embodiment 7
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.8 ︰, 0.1 ︰, 0.1 ︰ 0.9, gets Mg (OH) 2, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) step (1) gained compound is warming up to 1300 ℃, is incubated 2 hours, again naturally cooling;
(3) with step (2) gained compound, place H 2+ N 2Under the environment of reducing gas, under 1200 ℃, be incubated 1 hour, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 0.8Eu 0.1Mn 0.1Al (PO 4) 0.9The phosphoric acid magnalium fluorescent material of the europium ion of O and mn ion codoped.
Embodiment 8
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.99 ︰, 0.005 ︰, 0.005 ︰ 1.2, gets MgCO 3, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) with step (1) gained compound, place under the environment of CO reducing gas, be warming up to 1000 ℃, be incubated 4 hours, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 0.99Eu 0.005Mn 0.005Al (PO 4) 1.2The phosphoric acid magnalium fluorescent material of the europium ion of O and mn ion codoped.

Claims (4)

1. the phosphoric acid magnalium fluorescent material of europium ion and mn ion codoped is characterized in that: comprise that chemical constitution formula is Mg 1-x-yEu xMn yAl (PO 4) zThe component of O, wherein, x=0.001～0.1, y=0.001～0.1, z=0.9～1.2.
2. the preparation method of the phosphoric acid magnalium fluorescent material of europium ion and mn ion codoped is characterized in that through following each step:
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.8～0.998 ︰, 0.001～0.1 ︰, 0.001～0.1 ︰ 0.9～1.2, gets magnesium-containing compound, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) step (1) gained compound is warming up to 1000～1400 ℃, is incubated 0.5～4 hour, again naturally cooling;
(3) with step (2) gained compound, place CO or H 2+ N 2Under the environment of reducing gas, under 800 ~ 1300 ℃, be incubated 0.5～2 hour, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 1-x-yEu xMn yAl (PO 4) zThe phosphoric acid magnalium fluorescent material of the europium ion of O and mn ion codoped.
3. the preparation method of the phosphoric acid magnalium fluorescent material of europium ion and mn ion codoped is characterized in that through following each step:
(1) presses Mg Li ︰ Eu Li ︰ Mn Li ︰ AlPO 4Mol ratio is 0.8～0.998 ︰, 0.001～0.1 ︰, 0.001～0.1 ︰ 0.9～1.2, gets magnesium-containing compound, AlPO 4, Eu 2O 3, MnCO 3, mix;
(2) with step (1) gained compound, place CO or H 2+ N 2Under the environment of reducing gas, be warming up to 1000～1400 ℃, be incubated 0.5～4 hour, treat naturally cooling after, promptly obtaining chemical constitution formula is Mg 1-x-yEu xMn yAl (PO 4) zThe phosphoric acid magnalium fluorescent material of the europium ion of O and mn ion codoped.
4. according to claim 2 or 3 described preparation methods, it is characterized in that: described magnesium-containing compound is MgO, MgCO 3, Mg (HCO 3) OH, Mg (OH) 2In one or several.
CN201110246959XA 2011-08-26 2011-08-26 Europium ion and manganese ion-codoped magnesium aluminum phosphate fluorescent powder and preparation method thereof Pending CN102277166A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201110246959XA CN102277166A (en) 2011-08-26 2011-08-26 Europium ion and manganese ion-codoped magnesium aluminum phosphate fluorescent powder and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201110246959XA CN102277166A (en) 2011-08-26 2011-08-26 Europium ion and manganese ion-codoped magnesium aluminum phosphate fluorescent powder and preparation method thereof

Publications (1)

Publication Number Publication Date
CN102277166A true CN102277166A (en) 2011-12-14

Family

ID=45102908

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201110246959XA Pending CN102277166A (en) 2011-08-26 2011-08-26 Europium ion and manganese ion-codoped magnesium aluminum phosphate fluorescent powder and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102277166A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104629762A (en) * 2015-02-05 2015-05-20 洛阳理工学院 Europium-ion/manganese-ion-codoped barium yttrium phosphate red fluorescent powder and preparation method thereof
CN110591707A (en) * 2019-09-05 2019-12-20 常州工程职业技术学院 Mn (manganese)2+Activated vanadium phosphate inorganic fluorescent powder and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KI HYUK KWON ET AL.: "Luminescence Properties and Energy Transfer of Site-Sensitive Ca6-x-yMgx-z(PO4)4:Euy2+,Mnz2+ Phosphors and Their Application to Near-UV LED-Based White LEDs", 《INOGANIC CHEMISTRY》 *
YUANYUAN XU ET AL.: "A novel blue-emitting phosphor MgAl(PO4)O: Eu2+ for white LEDs", 《ADVANCED MATERIALS RESEARCH》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104629762A (en) * 2015-02-05 2015-05-20 洛阳理工学院 Europium-ion/manganese-ion-codoped barium yttrium phosphate red fluorescent powder and preparation method thereof
CN110591707A (en) * 2019-09-05 2019-12-20 常州工程职业技术学院 Mn (manganese)2+Activated vanadium phosphate inorganic fluorescent powder and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN104726101B (en) White light LEDs single-substrate white launches fluorophosphate fluorescent material and preparation method
CN101346452A (en) Yellow light-emitting phosphor and white light-emitting device using same
CN101824321B (en) Blue light excitation-based fluorescent powder for white light LED and preparation method thereof
CN101331578A (en) Silicate-based green phosphors
CN101851508B (en) Europium activated silicate green fluorescent powder and application thereof in white light emitting diode
JPWO2007029369A1 (en) Phosphor for light emitting diode
CN102391859A (en) Green fluorescent powder for white LED (light-emitting diode) use, its preparation method and application
CN101880528A (en) Single-matrix white fluorescent powder, manufacturing method thereof and light emitting device manufactured thereby
US8207661B2 (en) Borate phosphor and white light illumination device utilizing the same
CN102559179A (en) Single-matrix white light fluorescent powder for white light light-emitting diode (LED) and preparation method thereof
CN102277167B (en) Europium ion-doped aluminum magnesium phosphate fluorescent powder and preparation method thereof
CN104498031B (en) A kind of phosphate yellow fluorescent powder and preparation method thereof for white light LEDs
CN102786929B (en) Red phosphor
CN105062472B (en) A kind of preparation method and application of the blue colour fluorescent powder for warm white LED
CN101760191B (en) High-brightness barium-silicate-based blue-green fluorescent powder for LED and high-temperature reducing preparation method thereof
CN102277166A (en) Europium ion and manganese ion-codoped magnesium aluminum phosphate fluorescent powder and preparation method thereof
CN101608117B (en) Chlorborate-base phosphor powder used in light-emitting diodes
CN101519591B (en) Green fluorescent powder for white light LED suitable for blue light excitation and preparation method thereof
CN101012375A (en) Rare earth red fluorescent powder and preparing method thereof
CN104152142B (en) A kind of red fluorescence material and preparation method thereof
US20090160316A1 (en) Phosphors and lighting apparatus using the same
CN102533265B (en) Phosphate yellow fluorescent powder excited by blue light and preparation method thereof
CN101942301B (en) Phosphate red fluorescent powder for light-emitting diode and preparation method thereof
CN106085421A (en) A kind of Eu3+positive magnesium silicate potassium fluorescent material activated and its preparation method and application
CN100462621C (en) Luminous diode transmitting white light

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20111214