CN109988568A - A kind of nitrogen oxides green long afterglow luminescent material and preparation method thereof - Google Patents

A kind of nitrogen oxides green long afterglow luminescent material and preparation method thereof Download PDF

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CN109988568A
CN109988568A CN201910277227.3A CN201910277227A CN109988568A CN 109988568 A CN109988568 A CN 109988568A CN 201910277227 A CN201910277227 A CN 201910277227A CN 109988568 A CN109988568 A CN 109988568A
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green
nitrogen oxides
long
afterglow
long afterglow
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刘泉林
纪维涛
宋振
赵静
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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
    • C09K11/7734—Aluminates
    • 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
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7792—Aluminates

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Abstract

A kind of nitrogen oxides green long afterglow luminescent material, chemical constitution formula are as follows: M3‑3x‑3ySi13Al3O2N21: 3xC, 3yD, wherein M is Ca, and Sr's, Ba is one or more, C Ce3+Or Eu2+, D Dy3+,Tm3+,Ho3+,Nd3+One of, 0.001≤x≤0.1,0≤y≤0.1.The green nitrogen oxides long-afterglow material preparation method is to be calculated and weighed to mix in glove box after each raw material dosage by each element stoichiometric ratio according to composition formula, under nitrogen atmosphere, 0.1-2.0Mpa pressure, heat the mixture to 1600-2000 DEG C, 2-10h is kept the temperature, cools to room temperature with the furnace.The present invention is capable of emitting to continue visible green twilight sunset after ultraviolet light, and persistence reaches 1-60min, the green long afterglow material with Si, Al, O, N for basic matrix element, with Eu2+For afterglow center, and the trap number by increasing host material itself, realize the adjusting of long-persistence luminous intensity, thermal stability with higher and chemical stability.

Description

A kind of nitrogen oxides green long afterglow luminescent material and preparation method thereof
Technical field
The invention belongs to luminescent material technical field, it is related to a kind of nitrogen oxides green long afterglow luminescent material and its preparation Method.
Background technique
Long-afterglow material can absorb the energy of extraneous radiation and be stored, and remain to after stopping irradiation after supervention Light is therefore widely used in Emergency Light and display, the fields such as aviation, automobile instrument display panel.With regard to the body of long-afterglow material For system, early stage traditional long-afterglow material is concentrated mainly on ZnS, CaS sulfides system, and that there are stability is poor for the system, The deficiencies of easily decomposition, hygroscopicity are by force, afterglow performance is weak.Subsequent aluminates system is widely studied and develops, wherein SrAl2O4:Eu2+, Dy3+Green light long-afterglow material becomes current main commercial long-afterglow material, and there is chemical property to stablize, remaining The advantages that luminance is high, and persistence is long, but the problem of there are still poor water resistances.In order to solve this problem, chemical property it is stable, Water resistance becomes the hot spot of long-afterglow material exploitation in recent years, but the system afterglow better than the silicate systems of aluminate Intensity and duration are still to be improved.Therefore, the excellent green long afterglow luminescent material of research and development properties has important section Learn meaning and application background.
Summary of the invention
The present invention provides a kind of nitrogen oxides green long afterglow luminescent material, can produce green under 250-500nm excitation Long afterglow, persistence reaches 1-60min, and its particle is in the sheet of rule.
It is a further object to provide the preparation method of above-mentioned long-afterglow material, pressure 0.1-2.0Mpa, temperature A kind of green long afterglow material that performance is more stable is obtained at 1600 DEG C -2000 DEG C of degree.
To achieve the above object, the technical scheme adopted by the invention is that:
A kind of nitrogen oxides green long afterglow material, it is characterised in that: its chemical constitution formula are as follows: M3-3x-3ySi13Al3O2N21: 3xC, 3yD, wherein M is Ca, and Sr's, Ba is one or more, C Ce3+Or Eu2+, D Dy3+,Tm3+,Ho3+,Nd3+In one Kind, 0.001≤x≤0.1,0≤y≤0.1.
The excitation spectrum range of the green nitride long-afterglow material is in 250-500nm, and emission spectrum range is in 430- 600nm, peak value are adjustable in 460-540nm.
Its structure is monocline P1121(No.4), MX4(M=Si, Al；X=N, O) tetrahedron concurrent, side connects structure altogether At basic framework, cationic Ca2+,Sr2+,Ba2+One or more be present among hole as charge compensations.
Another technical solution of the present invention is: a kind of preparation side of nitrogen oxides green long afterglow luminescent material Method specifically sequentially includes the following steps:
(1) according to chemical constitution formula M3-3x-3ySi13Al3O2N21: 3xC, 3yD, wherein M is Ca, one kind of Sr, Ba or more Kind, C Ce3+Or Eu2+, D Dy3+,Tm3+,Ho3+,Nd3+One of, 0.001≤x≤0.1,0≤y≤0.1；By each member Plain stoichiometric ratio is calculated and is weighed including SiO2, Si3N4, AlN and Ca3N2、Sr3N2、Ba3N2One of or a variety of, DN3, CN3Dosage；
(2) in glove box, weighed each raw material is placed on tungsten crucible with the uniform ground and mixed of mortar, in nitrogen gas Under atmosphere, 0.1-2.0Mpa pressure, 1600-2000 DEG C is heated the mixture to, 2-10h is kept the temperature, cools to room temperature with the furnace；
(3) the obtained powder of step 2 is ground, obtains green nitrogen oxides long-afterglow material powder.
The present invention is capable of emitting to continue visible green twilight sunset after ultraviolet light, and persistence reaches 1-60min, this is remaining The wavelength that the twilight sunset spectrum of brightness material has be 460-540nm, can realize the adjustable of wavelength in a certain range, at the same have compared with High thermal stability and chemical stability.It can be effectively used for luminous mark material, photoelectric information, field wLEDs etc..
Detailed description of the invention
Fig. 1 is the embodiment of the present invention 1, embodiment 2, the XRD spectrum of long after glow luminous material made from embodiment 3；
Fig. 2 is that the excitation of long after glow luminous material made from the embodiment of the present invention 1 and transmitting are schemed；
Fig. 3 is the decay of afterglow curve graph of long after glow luminous material made from the embodiment of the present invention 1；
Fig. 4 is that the excitation of long after glow luminous material made from the embodiment of the present invention 2 and transmitting are schemed；
Fig. 5 is the decay of afterglow curve graph of long after glow luminous material made from the embodiment of the present invention 2；
Fig. 6 is that the excitation of long after glow luminous material made from the embodiment of the present invention 3 and transmitting are schemed；
Fig. 7 is the decay of afterglow curve graph of long after glow luminous material made from the embodiment of the present invention 3.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, embodiments of the present invention are not limited thereto.
Embodiment 1: the present embodiment chemical constitution formula is Sr2.97Si13Al3O2N21:0.03Eu2+Green long afterglow shine material Material the preparation method is as follows:
By chemical constitution formula Sr2.97Si13Al3O2N21:0.03Eu2+Stoichiometric ratio weighs SiO respectively2, Sr3N2, Si3N4, AlN, EuN high purity powdered form raw material are placed in agate mortar and are fully ground in the glove box full of protective atmosphere, fills raw material Divide and is uniformly mixed.Mixed raw material is transferred in tungsten crucible.Tungsten crucible is placed in high temperature and pressure graphite furnace in 1600-2000 DEG C Sintering 2-10h hours, takes out after natural cooling, regrinds, single-phase Sr can be obtained2.97Si13Al3O2N21:0.03Eu2+'s Fluorescent powder.
Nitrogen oxides green long afterglow luminescent material powder x-ray diffraction (XRD) map manufactured in the present embodiment as shown in Figure 1, Excitation, emission spectrum are as shown in Figure 2.Excitation peak is located at 400nm, and transmitting band is located at 430~680nm, and emission peak is located at 510nm, Belong to Eu2+4f65d1→4f7Transition.With ultraviolet light irradiation, stop observing in the dark in a period of time after irradiating, material is in Existing green afterglow.Fig. 3 is the decay of afterglow curve graph of the luminescent material, it is seen that the luminescent material can be held Supervention goes out the distinguishable light emission luminance of human eye in 0.32mcd/m2Above visible light.
Embodiment 2: the present embodiment chemical constitution formula is Sr1.47Ca1.5Si13Al3O2N21:0.03Eu2+Green long afterglow hair Luminescent material the preparation method is as follows:
By chemical constitution formula Sr1.47Ca1.5Si13Al3O2N21:0.03Eu2+Stoichiometric ratio weighs SiO respectively2, Sr3N2, Ca3N2, Si3N4, AlN, EuN high purity powdered form raw material, be placed in agate mortar full of protective atmosphere glove box in sufficiently grind Mill, is sufficiently mixed raw material uniformly.Mixed raw material is transferred in tungsten crucible.By tungsten crucible be placed in high temperature and pressure graphite furnace in 1600-2000 DEG C sintering 2-10h hours, taken out after natural cooling, regrind, single-phase can be obtained Sr1.47Ca1.5Si13Al3O2N21:0.03Eu2+Fluorescent powder.
Nitrogen oxides green long afterglow luminescent material powder x-ray diffraction (XRD) map manufactured in the present embodiment as shown in Figure 1, Excitation, emission spectrum are as shown in Figure 4.Excitation peak is located at 400nm, and transmitting band is located at 430~680nm, and emission peak is located at 480nm, Belong to Eu2+4f65d1→4f7Transition.With ultraviolet light irradiation, stop observing in the dark in a period of time after irradiating, material is in Existing green afterglow.Fig. 5 is the decay of afterglow curve graph of the luminescent material, it is seen that the luminescent material can be held Supervention goes out the distinguishable light emission luminance of human eye in 0.32mcd/m2Above visible light.
Embodiment 3: the present embodiment chemical constitution formula is Sr1.47Ba1.5Si13Al3O2N21:0.03Eu2+Green long afterglow hair Luminescent material the preparation method is as follows:
By chemical constitution formula Sr1.47Ba1.5Si13Al3O2N21:0.03Eu2+Stoichiometric ratio weighs SiO respectively2, Sr3N2, Ba3N2, Si3N4, AlN, EuN high purity powdered form raw material, be placed in agate mortar full of protective atmosphere glove box in sufficiently grind Mill, is sufficiently mixed raw material uniformly.Mixed raw material is transferred in tungsten crucible.By tungsten crucible be placed in high temperature and pressure graphite furnace in 1600-2000 DEG C sintering 2-10h hours, taken out after natural cooling, regrind, single-phase can be obtained Sr1.47Ba1.5Si13Al3O2N21:0.03Eu2+Fluorescent powder.
Nitrogen oxides green long afterglow luminescent material powder x-ray diffraction (XRD) map manufactured in the present embodiment as shown in Figure 1, Excitation, emission spectrum are as shown in Figure 6.Excitation peak is located at 400nm, and transmitting band is located at 430~680nm, and emission peak is located at 535nm, Belong to Eu2+4f65d1→4f7Transition.With ultraviolet light irradiation, stop observing in the dark in a period of time after irradiating, material is in Existing green afterglow.Fig. 7 is the decay of afterglow curve graph of the luminescent material, it is seen that the luminescent material can be held Supervention goes out the distinguishable light emission luminance of human eye in 0.32mcd/m2Above visible light.
Embodiment 4 to embodiment 12 according in table 1 chemical constitution formula and stoichiometric ratio weigh required raw material, prepare Method is same as Example 1, and the emission peak positions of synthesized sample and persistence are listed in table 1.
Table 1
Embodiment Chemical constitution formula Emit peak wavelength (nm) Persistence (s)
Comparative example 1 Sr2.97Si13Al3O2N21:0.03Eu2+ 510nm 1700s
4 Sr2.985Si13Al3O2N21:0.015Eu2+ 495nm 1380s
5 Sr2.91Si13Al3O2N21:0.09Eu2+ 510nm 1080s
6 Sr2.955Si13Al3O2N21:0.03Eu2+,0.015Dy3+ 503nm 1960s
7 Sr1.485Ca1.5Si13Al3O2N21:0.015Eu2+ 470nm 1340s
8 Sr1.41Ca1.5Si13Al3O2N21:0.09Eu2+ 492nm 1180s
9 Sr1.455Ca1.5Si13Al3O2N21:0.03Eu2+,0.015Dy3+ 480nm 1600s
10 Sr1.485Ba1.5Si13Al3O2N21:0.015Eu2+ 525nm 1320s
11 Sr1.41Ba1.5Si13Al3O2N21:0.09Eu2+ 540nm 1260s
12 Sr1.455Ba1.5Si13Al3O2N21:0.03Eu2+,0.015Dy3+ 535nm 1560s
Specific case used herein is expounded embodiments of the present invention, and the explanation of above embodiments is only used In facilitating the understanding of the method and its core concept of the invention.It should be pointed out that for the ordinary person of the art, not , can be with several improvements and modifications are made to the present invention under the premise of being detached from the principle of the invention, these improvement and modification are also fallen into In the protection scope of the claims in the present invention.

Claims (4)

1. a kind of nitrogen oxides green long afterglow luminescent material, it is characterised in that: its chemical constitution formula are as follows: M3-3x- 3ySi13Al3O2N21: 3xC, 3yD, wherein M is Ca, and Sr's, Ba is one or more, C Ce3+Or Eu2+, D Dy3+,Tm3+,Ho3 +,Nd3+One of, 0.001≤x≤0.1,0≤y≤0.1.
2. a kind of nitrogen oxides green long afterglow material according to claim 1, it is characterised in that: the green nitride is long For the excitation spectrum range of afterglowing material in 250-500nm, emission spectrum range can in 460-540nm in 430-600nm, peak value It adjusts.
3. a kind of nitrogen oxides green long afterglow material according to claim 1 or 2, it is characterised in that: its structure is single Biassed fabric P1121, wherein P1121For No.4 space group, MX4, wherein M=Si, Al；X=N, O tetrahedron concurrent, side connects structure altogether At basic framework, cationic Ca2+,Sr2+,Ba2+One or more be present among hole as charge compensations.
4. a kind of preparation method of nitrogen oxides green long afterglow material, it is characterised in that: specific step is as follows:
(1) according to chemical constitution formula M3-3x-3ySi13Al3O2N21: 3xC, 3yD, wherein M is Ca, and Sr's, Ba is one or more, and C is Ce3+Or Eu2+, D Dy3+,Tm3+,Ho3+,Nd3+One of, 0.001≤x≤0.1,0≤y≤0.1；By each element chemistry Metered proportions are calculated and are weighed including SiO2, Si3N4, AlN and Ca3N2、Sr3N2、Ba3N2One of or a variety of, DN3, CN3's Dosage；
(2) in glove box, weighed each raw material is placed on tungsten crucible with the uniform ground and mixed of mortar, nitrogen atmosphere, Under 0.1-2.0Mpa pressure, 1600-2000 DEG C is heated the mixture to, 2-10h is kept the temperature, cools to room temperature with the furnace；
(3) the obtained powder of step (2) is ground, obtains green nitrogen oxides long-afterglow material powder.
CN201910277227.3A 2019-04-08 2019-04-08 A kind of nitrogen oxides green long afterglow luminescent material and preparation method thereof Pending CN109988568A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN102952541A (en) * 2011-08-24 2013-03-06 株式会社东芝 Luminescent material
CN104103743A (en) * 2013-04-03 2014-10-15 株式会社东芝 Light emitting device
US20160068747A1 (en) * 2014-09-05 2016-03-10 Kabushiki Kaisha Toshiba Phosphor, method for producing the same, and light-emitting device using the same
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Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102952541A (en) * 2011-08-24 2013-03-06 株式会社东芝 Luminescent material
CN102719244A (en) * 2012-06-25 2012-10-10 重庆文理学院 Secondarily-excited type silicon-aluminate long-afterglow fluorescent powder and preparation method thereof
CN104103743A (en) * 2013-04-03 2014-10-15 株式会社东芝 Light emitting device
US20160068747A1 (en) * 2014-09-05 2016-03-10 Kabushiki Kaisha Toshiba Phosphor, method for producing the same, and light-emitting device using the same
CN106281324A (en) * 2016-08-10 2017-01-04 北京科技大学 Long after glow luminous material that a kind of persistence is controlled and preparation method thereof

Non-Patent Citations (2)

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