CN1266083A - Long afterglow phosphorescent material - Google Patents

Long afterglow phosphorescent material Download PDF

Info

Publication number
CN1266083A
CN1266083A CN 98124888 CN98124888A CN1266083A CN 1266083 A CN1266083 A CN 1266083A CN 98124888 CN98124888 CN 98124888 CN 98124888 A CN98124888 A CN 98124888A CN 1266083 A CN1266083 A CN 1266083A
Authority
CN
China
Prior art keywords
long
phosphor material
chemical expression
decay phosphor
compound
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.)
Granted
Application number
CN 98124888
Other languages
Chinese (zh)
Other versions
CN1116377C (en
Inventor
顾中球
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to CN 98124888 priority Critical patent/CN1116377C/en
Publication of CN1266083A publication Critical patent/CN1266083A/en
Application granted granted Critical
Publication of CN1116377C publication Critical patent/CN1116377C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Landscapes

  • Luminescent Compositions (AREA)

Abstract

A new alkaline earth phosphoaluminic acid long-afterglow phosphorescent material containing Eu(2+), Dy (3+) and Ce (3+) as additional activating agents is characterized by that its chemical expression formula is (M1-xEux)O.a(Al1-y-z DyyCez)O3.bP2O5, where M represents at least one element of Sr, Mg, Ca and Ba, and its production method adopts the solid reaction at high-temp. for preparation, its raw materials, utilize their correspondent oxides, and the dosages of them are defined according to the chemical expression formula. Said invented product possesses high crystallinity, chemical stability and initial brightness and long afterglow time, and is suitable for low illumination light display, mark and decoration in dark environment.

Description

Long-decay phosphor material
The present invention relates to a kind of long after glow luminous material, specially refer to a kind of new europium (Eu 2+) activate dysprosium (Dy 3+) and cerium (Ce 3+) as the alkaline earth aluminophosphates long-decay phosphor material of additional activation agent.
Luminophore is exciting the light that stops the back emission to be called twilight sunset.The general luminescent material that twilight sunset is very short is called fluorescent material, and the phosphor material that calls of twilight sunset length.From luminescence mechanism, excitation energy directly (or through transmission ofenergy) converts the radiative fluorescence that is called to, and excitation energy then converts the radiative phosphorescence that is called to through storage.Phosphor material particularly long-decay phosphor material has important use in modern society, for example shows in low-light (level), and the aspects such as decoration in sign mark and the dark surrounds all have been widely used.
Used more is copper activated zinc sulphide in the past, ZnS:Cu.The emission wavelength of ZnS:Cu is 530nm, is in the higher range of wavelengths of eye sensitivity curve luminous efficiency, and higher luminous efficiency is arranged.But fall short of its persistence, and twilight sunset just can not be observed after dozens of minutes.And copper activated zinc sulphide chemical property is stable inadequately, is exposed to for a long time can decompose in the air to destroy, and body colour can blackening.Like this, material just is difficult in outdoor utility.
In order to improve the characteristic of zinc sulphide class long-afterglow material, people have done research to adding rare ion of going up in the zinc sulphide matrix, it is said some shortcoming [Mao Xianghui etc. that can overcome zinc sulphide class phosphor material, Hunan Normal University＜natural science journal 〉, Vol.14 (1), 47,1991; Vol.15 (2), 145,1992].
Different with zinc sulphide class material, inorganic oxysalt is often more stable on chemical property.Eu activated strontium aluminate SrAl 2O 4: Eu has the emission wavelength similar to ZnS:Cu, long twilight sunset is also arranged, but after-glow brightness is lower.The component proportioning that changes strontium aluminate can make luminous efficiency and after-glow brightness make moderate progress, but amplitude little (V.Abbruscato, J.Electrochem.Soc., Vol.118,930,1971).Some rare earth ion is added SrAl as the additional activation agent 2O 4: Eu, can provide the degree of depth more shallow hole trap energy level, improve persistence characteristic (H.Yamamoto et al., J.Electrochem., Vol.143 (1996) 2670-2673 significantly; E.Nakaxawa et al., J.Lumin.Vol.72-74,236,1997).According to this mechanism, the material of exploitation has MOa (Al 1.bB b) 2O 3: xR (US 5376303) and MAl 2O 4: Eu, R (US 5424001), wherein M represents alkaline-earth metal, and R represents rare earth ion.
Above-mentioned materials is greatly improved than zinc sulphide class long-afterglow material at after-glow brightness with on the time length, and the aerial stability of material is also better.But, because strontium aluminate SrAl 2O 4Or the meeting decomposition in water of alkaline earth aluminate class, its range of application is restricted.And, on mechanism, also only limit to the more shallow rare earth ion of hole trap energy level (being mainly Dy and Nd), the brightness of twilight sunset and time length are limited to.
Purpose of the present invention: provide a kind of new europium (Eu 2+) activate dysprosium (Dy 3+) and cerium (Ce 3+) as the alkaline earth phosphorus aluminic acid long-decay phosphor material of additional activation agent.The high-brightness long persistence material that this is a kind of after-glow brightness height, longer duration, the materials chemistry performance is stable, its excitation spectrum can extend to visible yellow band from the ultraviolet waves district.Be applicable to that low-light (level) shows the aspects such as decoration in light, industrial art, sign mark and the dark surrounds, not only have enjoying value, also have energy-saving effect, so arranged wide development prospect.
To achieve these goals, invention scheme of the present invention is: a kind of long-decay phosphor material, and its main chemical expression is as follows:
(M 1-xEu x) Oa (Al 1-y-zDy yCe z) 2O 3BP 2O 5(1) in the formula: M represents Sr, Mg, and at least a element among Ca and the Ba, again
0＜x≤0.2
0＜y≤0.2
0＜z≤0.05
0.7≤a≤2
0＜b≤0.5
Characteristics of the present invention: the chemical reaction basis of long-decay phosphor material is that phosphorus partly replaces aluminium, forms a kind of new alkaline earth aluminophosphates.This material has higher degree of crystallinity and chemical stability, and higher original intensity is arranged, and on phosphorescence mechanism, the present invention adopts Dy 3+And Ce 3+As additional activation agent, Dy 3+Provide more shallow trap level, Ce 3+Darker trap level is provided.The hole that deep energy level is caught can be made staged by the shallow trap energy level and discharge, thereby makes Eu 2+Persistence longer.According to the material that the present invention makes, high original intensity and after-glow brightness are arranged, arranged long time of persistence.
Making method of the present invention:
One, adopt the solid reacting method under the high temperature to produce alkaline earth aluminophosphates long persistence phosphor of the present invention, its raw material is the compound that adopts corresponding oxide compound or at high temperature can transform into oxide compound, promptly uses Eu 2O 3, Dy 2O 3, CeO, MgO or MgCO 3, CaCO 3, BaCO 3Or Ba (OH) 2, SrCO 3, Al 2O 3Or AlF 33H 2O, (NH 4) 2HPO 4Or NH 4H 2PO 4, its consumption is according to the coefficient scope of forming each elemental composition in the chemical expression (1), determines the usage quantity of above-mentioned oxide compound or compound.Its making step is: earlier with rare earth oxide Eu 2O 3, Dy 2O 3Directly mix with CeO, or use HNO 3After the dissolving, make the oxalate precipitation thing, become to mix rare oxide compound of going up, mix the same again Al of its mixture with forming desired alkaline-earth oxide in the formula (1) or adding carbonate then in 1000-1100 ℃ of thermolysis 2O 3(NH 4) 2HPO 4(or NH 4H 2PO 4) uniform mixing, in 1100-1400 ℃ at N 2/ H 2Or in the reducing atmosphere of powdered carbon, calcination 1-4 hour, sieve through pulverizing ball milling then, promptly be made into alkaline earth aluminophosphates long-decay phosphor material of the present invention.As use solubility promoter, for example (H 3BO 3), can promote the formation of phosphorescent substance.
Two, also can adopt the two-step method making access method, be about to raw mix at first in air in 1000-1400 ℃ in stove calcination 1-3 hour, the calcination thing after pulverizing ball milling and sieving, again under reducing atmosphere in 1100-1400 ℃ of calcination 2-4 hour.Two-step approach can obtain the same good long-decay phosphor material of performance.
Description of drawings:
Fig. 1 is (M 0.99Eu 0.01) O1.01 (Al 0.99Dy 0.0098Ce 0.0002) 2O 30.005P 2O 5Excite room temperature emmission spectrum down at the 254nmHg line.
Fig. 2 is (M 0.99Eu 0.01) O0.96 (Al 0.9895Dy 0.01Ce 0.0005) 2O 30.01P 2O 5Under the 254nmHg line excites, excite and stop back 10 minutes room temperature emmission spectrum.
Below provide embodiment:
Example 1, with 1.76 the gram Eu 2O 3(0.005 mole), 3.73 gram Dy 2O 3(0.01 mole) and 0.031 gram CeO (2 * 10 -4Mole) uses HNO 3After the dissolving, make the oxalate precipitation thing,, obtain mixed rare-earth oxide, again it is restrained SrCO with 143.2 in 1100 ℃ of heating 1 hour 3(0.97 mole), 0.99 gram BaCO 3(0.005 mole), 1 gram CaCO 3(0.01 mole) and 0.2 gram MgO (0.005 mole) mix, and said mixture is with 102 gram Al 2O 3(1.00 moles) and 0.53 gram (NH 4) 2HPO 4(0.004 mole) and 6.2 gram H 3BO 3(0.1 mole) mixes, and ball milling 12 hours, then, put into corundum crucible in 1300 ℃ at N 2/ H 2Or calcination 3 hours under the reducing atmosphere of powdered carbon.The product that calcination obtains is pulverized ball milling with ordinary method, and 200 orders sieve and obtain:
(M 0.99Eu 0.01) O1.01 (Al 0.99Dy 0.0098Ce 0.0002) 2O 30.005P 2O 5M=0.97Sr+0.01Ca+0.005Ba+0.005Mg in the formula.
Excite down at the 254nmHg line, its brightness is SrAl 2O 4: 0.01Eu, 102% of 0.01Dy.
Example 2-7, identical with the preparation method of example 1, but the P content difference in the component raw material, the test result of the phosphorescent substance that makes is as shown in table 1.Brightness means the original intensity of 254nmHg line under exciting in the table.Table 1
Example Phosphorescent substance Brightness
?1 (M 0.99Eu 0.01)O·1.01(Al 0.99Dy 0.0098Ce 0.0002) 2O 3·0.002P 2O 5 ?102
?2 (M 0.99Eu 0.01)O·1.01(Al 0.99Dy 0.0098Ce 0.0002) 2O 3·0.005P 2O 5 ?105
?3 (M 0.99Eu 0.01)O·1.01(Al 0.99Dy 0.0098Ce 0.0002) 2O 3·0.01P 2O 5 ?110
?4 (M 0.99Eu 0.01)O·1.01(Al 0.99Dy 0.0098Ce 0.0002) 2O 3·0.02P 2O 5 ?110
?5 (M 0.99Eu 0.01)O·1.01(Al 0.99Dy 0.0098Ce 0.0002) 2O 3·0.05P 2O 5 ?107
?6 (M 0.99Eu 0.01)O·1.01(Al 0.99Dy 0.0098Ce 0.0002) 2O 3·0.1P 2O 5 ?104
?7 (M 0.99Eu 0.01)O·1.01(Al 0.99Dy 0.0098Ce 0.0002) 2O 3·0.2P 2O 5 ?100
Contrast SrAl 2O 4∶0.01Eu，0.01Dy ?100
Wherein, the sample that obtains of example 3 for the emmission spectrum under the 254nmHg line excites referring to Fig. 1.
Example 8, the processing method that provides by example 1 preparation, but component element and relative content thereof change, and the material formula is:
(M 0.99Eu 0.01) O0.96 (Al 0.9895Dy 0.01Ce 0.0005) 2O 30.001P 2O 5M=0.99Sr+0.01Ca in the formula.According to 10 minutes, the twilight sunset spectrum that stops to excite record in back 10 minutes was seen Fig. 2 to this sample through the 254nmHg wire spoke.
Example 9-10 presses the processing method preparation that example 1 proposes, but component element and relative content thereof change to some extent, and the test result of the phosphor material that makes is as shown in table 2.Table 2
Example Phosphorescent substance After-glow brightness
?8 (M 0.99Eu 0.01)O·0.96(Al 0.9895Dy 0.01Ce 0.0005) 2O 3·0.01P 2O 5 ?106
?9 (M 0.99Eu 0.01)O·0.96(Al 0.989Dy 0.01Ce 0.001) 2O 3·0.01P 2O 5 ?107
?10 (M 0.99Eu 0.01)O·0.96(Al 0.988Dy 0.01Ce 0.002) 2O 3·0.01P 2O 5 ?106
Contrast SrAl2O4∶0.01Eu，0.01Dy ?100
*1、M＝0.99Sr+0.01Ca。* 2, after-glow brightness means the 254nmHg wire spoke according to 10 minutes, excite to stop the twilight sunset spectrographic integral area to record in back 10 minutes.

Claims (4)

1, a kind of new europium (Eu 2+), dysprosium (Dy 3+) and cerium (Ce 3+) as the alkaline earth aluminophosphates long-decay phosphor material of additional activation agent, its main chemical expression is as follows:
(M 1-xEu x) Oa (Al 1-y-zDy yCe z) 2O 3BP 2O 5(1) M represents Sr in the formula, Mg, and at least a element among Ca and the Ba, again
0＜x≤0.2
0＜y≤0.2
0＜z≤0.05
0.7≤a≤2
Chemical reaction in the above-mentioned chemical expression in 0＜b≤0.5 (1) is that phosphorus partly replaces aluminium, forms a kind of new alkaline earth aluminophosphates long-decay phosphor material.
2, long-decay phosphor material as claimed in claim 1 is characterized in that M represents Sr and Ca element in the chemical expression (1).
3, long-decay phosphor material as claimed in claim 1 is characterized in that M represents the Sr element in the chemical expression (1).
4, long-decay phosphor material making method as claimed in claim 1 is characterized in that adopting solid state reaction making method under the high temperature, and its raw material is the compound that adopts corresponding oxide compound or at high temperature can transform into oxide compound, promptly uses Eu 2O 3, Dy 2O 3, CeO, MgO or MgCO 3, CaCO 3, BaCO 3Or Ba (OH) 2, SrCO 3, Al 2O 3Or AlF 33H 2O, (NH 4) 2HPO 4Or NH 4H 2PO 4, its consumption is according to the coefficient scope of forming each elemental composition in the chemical expression (1), determines the usage quantity of above-mentioned oxide compound or compound.Its making step is: earlier with rare earth oxide Eu 2O 3, Dy 2O 3Directly mix with CeO, or use HNO 3After the dissolving, make the oxalate precipitation thing, become mixed rare-earth oxide, mix the same again Al of its mixture with forming desired alkaline-earth oxide in the formula (1) or adding carbonate then in 1000-1100 ℃ of thermolysis 2O 3(NH 4) 2HPO 4(or NH 4H 2PO 4) uniform mixing, in 1100-1400 ℃ of reducing atmosphere calcination 1-4 hour, sieve through pulverizing ball milling then, promptly be made into aluminophosphates long-decay phosphor material on the alkali of the present invention.
CN 98124888 1999-03-10 1999-03-10 Long afterglow phosphorescent material Expired - Fee Related CN1116377C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 98124888 CN1116377C (en) 1999-03-10 1999-03-10 Long afterglow phosphorescent material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 98124888 CN1116377C (en) 1999-03-10 1999-03-10 Long afterglow phosphorescent material

Publications (2)

Publication Number Publication Date
CN1266083A true CN1266083A (en) 2000-09-13
CN1116377C CN1116377C (en) 2003-07-30

Family

ID=5228881

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 98124888 Expired - Fee Related CN1116377C (en) 1999-03-10 1999-03-10 Long afterglow phosphorescent material

Country Status (1)

Country Link
CN (1) CN1116377C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105238403A (en) * 2012-06-25 2016-01-13 重庆文理学院 Fluorescent powder and preparation method therefor
CN110835262A (en) * 2019-11-20 2020-02-25 闽南师范大学 Blue-green hard luminous stone with zirconium-niobium ion common luminous center and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105238403A (en) * 2012-06-25 2016-01-13 重庆文理学院 Fluorescent powder and preparation method therefor
CN110835262A (en) * 2019-11-20 2020-02-25 闽南师范大学 Blue-green hard luminous stone with zirconium-niobium ion common luminous center and preparation method thereof
CN110835262B (en) * 2019-11-20 2022-04-05 闽南师范大学 Blue-green hard luminous stone with zirconium-neodymium ion common luminous center and preparation method thereof

Also Published As

Publication number Publication date
CN1116377C (en) 2003-07-30

Similar Documents

Publication Publication Date Title
EP1573826B1 (en) Illumination system comprising a radiation source and a fluorescent material
CN101273108B (en) Silicate phosphor for uv and long-wavelength excitation and preparation method thereof
CN102120931B (en) Red fluorophor and preparation method thereof
JP5362288B2 (en) Non-stoichiometric tetragonal copper alkaline earth silicate phosphor and method for producing the same
KR100304167B1 (en) Long afterglow light emitting material and its manufacturing method
EP2447338A1 (en) Borophosphate phosphor and light source
WO2007055538A1 (en) Copper-alkaline-earth-silicate mixed crystal phosphors
EP1922904A1 (en) Carbidonitridosilicate luminescent substance
CN115368893B (en) Sodium gadolinium gallium germanium garnet Dan Jiqing light fluorescent powder and preparation method thereof
CN102634339B (en) Red long-afterglow fluorescent material of alkaline earth titanate activated by Bi<2+> and preparation method thereof
CN102108297B (en) Red fluorescent powder, preparation method thereof and luminescent device prepared therefrom
CN111892924A (en) Cu ion doped gallate base orange red luminescent material and preparation method thereof
CN101760191B (en) High-brightness barium-silicate-based blue-green fluorescent powder for LED and high-temperature reducing preparation method thereof
CN1116377C (en) Long afterglow phosphorescent material
KR20050101151A (en) Synthesis of the phosphorescent phosphor of strontium barium aluminates
CN107474838B (en) Blue-green long-afterglow luminescent material and preparation method thereof
AU2021102695A4 (en) A POTENTIAL BLUE-EMITTING PHOSPHOR Na2CaSiO4: Eu2+, Ce3+ PHOSPHOR WITH TUNABLE EMISSION FOR UV/NUV BASED WHITE LED AND SOLAR APPLICATIONS
CN112480918B (en) Manganese-doped deep red light fluorescent powder material and preparation method thereof
CN114058371A (en) Yellow light long afterglow luminescent material and preparation method and application thereof
CN101372617A (en) Blue fluorescent powder for field emission and vacuum fluorescence display and preparation thereof
CN100368506C (en) Long-decay phosphor material and its prepn
CN101473013A (en) Thulium-containing fluorescent substance for white light emitting diode and manufacturing method thereof
KR100387659B1 (en) Manufacturing method of strontium aluminate phosphor by the sol-gel method
Mungmode et al. Luminescence in Eu2+ Activated (Ca5-xSrx)(PO4) 3Cl (x= 0.1, 2.4) Phosphors
CN109294576B (en) Single-ion doped white fluorescent powder applied to WLED device 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
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee