CN109554178A - The green-yellow light long-afterglow material and preparation method of afterglow property are improved by addition boron - Google Patents
The green-yellow light long-afterglow material and preparation method of afterglow property are improved by addition boron Download PDFInfo
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- CN109554178A CN109554178A CN201811472024.1A CN201811472024A CN109554178A CN 109554178 A CN109554178 A CN 109554178A CN 201811472024 A CN201811472024 A CN 201811472024A CN 109554178 A CN109554178 A CN 109554178A
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Abstract
A kind of green-yellow light long-afterglow material and preparation method improving afterglow property by addition boron, belongs to field of light emitting materials.Select gallium-aluminum garnet sill as matrix, using trivalent Ce as activator, trivalent Yb constitutes parent lattice as defect level trap center, Y, Al, Ga, O.Regulated and controled by addition boron-based compounds to the structure of long sunset glow material and with sunset glow performance in synthesis process, to obtain that a kind of crystal property is good, the sunset glow time is long, sunset glow intensity is high and excitation and the wider green-yellow light long-afterglow material of transmitting range.The long-afterglow material can effectively be excited by ultraviolet light and visible light, and excitation wavelength range is 300nm~500nm, emit green-yellow light, and launch wavelength range is 450nm~700nm.Boric acid or boron oxide are added in material as cosolvent, sample crystallization significantly improves, while boron ion enters parent lattice, its microstructure is adjusted, it is improved while improving the depth of defect level, while increasing the concentration of defect level, and then realize sunset glow time and intensity.
Description
Technical field
The invention belongs to luminescent material technical fields；It is related to a kind of crystallinity, persistence and sunset glow intensity while improves
Lighting display system can be particularly applicable to by the green-yellow light long-afterglow material that visible light effectively excites, the material.
Background technique
Long after glow luminous material has the function of " optical storage ".After by light irradiation, a part of luminous energy can be by its structure
In trap level capture, to be stored in the structure of the material, after irradiation, the energy of this section store is appropriate
Temperature under the conditions of will continue to release in luminous form, and then generate long afterglow.Currently, long after glow luminous material has very
It is a variety of, including aluminate, silicate and sulfide etc., wherein gallium-aluminum garnet base long persistence luminescent material is because of its excitation and hair
Penetrate that range is wide, structural stability is high, sunset glow superior performance and be concerned.
At present long-afterglow material be mainly used in safe emergency lighting show, instrument and daily necessities decoration etc.,
It also has great application prospect in terms of bio-imaging and information storage.The sunset glow performance of long after glow luminous material is generally logical
It crosses two ways to optimize: (1) selecting suitable host material, e.g., aluminate, garnet structure material；(2) in the material
Suitable rare earth or other metal ions are added, e.g., boron ion, silicon ion etc., for adjusting trap level depth and concentration, from
And improve long-persistence luminous time and sunset glow intensity.The synthetic method of long-afterglow material is also varied, including high temperature solid-state
Sintering process, combustion method, coprecipitation and sol-gal process etc..Wherein high-temperature solid-phase sintering method is at low cost, product purity is high
And process flow it is simple the advantages that and it is the most commonly used.
In recent years, we have done compared with in-depth study gallium-aluminum garnet base long persistence material at seminar, mainly regulate and control
Pattern improves sunset glow performance and explains its long-persistence luminous mechanism etc..Japanese Ueda et al. adds by ion
Defect level realizes the excellent long afterglow performance of the long sunset glow material of gallium-aluminum garnet base, but research object is mainly ceramic material,
The sintering process of transparent ceramic material requires height, and prevailing experimental conditions are unable to complete.We are with high temperature solid-state method sintering method
Further do the optimization of aspect of performance in basis.
Summary of the invention
The present invention provides what a kind of crystallinity, persistence and sunset glow intensity improved simultaneously effectively to be swashed by visible light
The green-yellow light long-afterglow material of hair.
The object of the invention first is that in the synthesis process addition boron-containing compound as cosolvent, for improving the material
Crystallinity.
The second object of the present invention is to the boron ion in boron-containing compound enters parent lattice, depth to defect level and dense
Degree is adjusted, and then improves its sunset glow performance.
The object of the invention third is that can effectively be excited by visible light for what crystallinity, persistence and sunset glow intensity improved
Green-yellow light long-afterglow material a kind of economical and practical synthetic method is provided.
The object of the invention fourth is that by comparing thermotropic excitation spectrum and photoexcitation spectrum it is long to gallium-aluminum garnet base more than
The defect capture mechanism of brightness material is made that intuitive explanation.
The present invention selects gallium-aluminum garnet sill as matrix, and using trivalent Ce as activator, trivalent Yb is as defect energy
Grade trap center, Y, Al, Ga, O constitute parent lattice.By addition boron-based compounds to the knot of long sunset glow material in synthesis process
Structure and regulated and controled with sunset glow performance, to obtain that a kind of crystal property is good, the sunset glow time is long, sunset glow intensity is high and excitation and hair
Penetrate the green-yellow light long-afterglow material of wider range.
A kind of crystallinity improves, while capable of effectively being excited by visible light of improving of persistence and sunset glow intensity is yellowish green
The chemical formula of light long-afterglow material are as follows: Y3-a-bAl2Ga3O12:aCe3+,bYb3+,xB3+, wherein 0.003≤a≤0.15,0.0015
≤ b≤0.15,0.001≤x≤10%, it may be preferable that the chemical formula of long-afterglow material of the invention are as follows: Y3-a-bAl2Ga3O12:
aCe3+,bYb3+,xB3+, wherein 0.015≤a≤0.09,0.003≤b≤0.03,0.005≤x≤10%, most preferably, this
The chemical formula of the long-afterglow material of invention are as follows: Y3-a-bAl2Ga3O12:aCe3+,bYb3+, xB3+, wherein a=0.015, b=
0.003,0.005≤x≤10%,
On the other hand, the present invention provides preparing a kind of crystallinity to improve, while persistence and sunset glow intensity improve
It can be included the following steps: by the method for the green-yellow light long-afterglow material that visible light effectively excites, this method
1) general formula Y is pressed3-a-bAl2Ga3O12:aCe3+,bYb3+,xB3+, corresponding raw material in the material is weighed, and mix equal
It is even, it is placed under air, reducing atmosphere or high pressure inert atmosphere and calcines, temperature is 1400~1600 DEG C, and the time is 3~6h；
2) the green-yellow light long-afterglow material that step 1) obtains is cleaned using deionized water, ethyl alcohol and diluted acid, and
After dry.
Further, in step 1), raw material can come from the oxide of yttrium, aluminium, gallium, cerium and ytterbium, and boron-based compounds can
To be boric acid or boron oxide.
The principle of the invention: in long after glow luminous material, boric acid or boron oxide reduce the sintering temperature of the material as cosolvent
Degree, while the crystallinity for improving material makes its particle increase to tens microns by several microns.
Boron ion in long after glow luminous material synthesis process in boric acid or boron oxide replaces a small amount of aluminium ion and occupies
Aluminium tetrahedral sites make host material Lattice Contraction, and defect in structure is caused to increase, so that defect level concentration is made to become larger, into
And make afterglow luminescence enhanced strength.
The boron ion in long after glow luminous material synthesis process in boric acid or boron oxide replaces a small amount of aluminium ion simultaneously simultaneously
Aluminium tetrahedral sites are occupied, its Lattice Contraction is made, form new deeper defect level, extend the sunset glow time, are obtained by dividing
(min) to the persistence of tens hours (h) magnitudes.It is captured by the defect level of long after glow luminous material and is used for afterglow luminescence
Energy, derived from light excitation after activation electronics.
Preparation method of the present invention is simple, easily operated, equipment cost is low and pollution-free.More than the preparation-obtained novel length
Brightness material can effectively be excited by visible light, excitation wavelength range be 300nm~500nm, launch wavelength range be 450nm~
700nm.Boric acid or boron oxide are added in the long sunset glow material of gallium-aluminum garnet base as cosolvent, sample crystallization significantly improves,
Boron ion enters the depth that parent lattice its microstructure is adjusted raising defect level simultaneously, while increasing defect level
Concentration, and then realize that sunset glow time and sunset glow intensity while improve.
Detailed description of the invention
Fig. 1 is X-ray powder (XRD) figure of long-afterglow material prepared by comparative example 1 and embodiment 1-5.
Y3Al2Ga3O12The XRD diagram of standard substance is also given at Fig. 1 as reference.
Fig. 2 is excitation spectrum (the monitoring wavelength X of sample segment in embodiment 1-5emFor 520nm) and emission spectrum (excitation
Wavelength XexFor 430nm) curve synoptic diagram.
Fig. 3 is the sunset glow attenuation curve of sample segment in comparative example 1 and embodiment 1-5.
Fig. 4 is the curve comparison of the thermotropic excitation spectrum of embodiment 2 and photoexcitation spectrum.
Specific embodiment
Comparative example 1
The component coefficient of long after glow luminous material is a=0.015, b=0.003, x=0.Raw material is pressed into chemical mol ratio
It weighs and is uniformly mixed, be placed under air, reducing gas or high pressure inert atmosphere and calcine, temperature is 1400~1600 DEG C, the time
For 4h.Firing sample is ground, is then cleaned using deionized water, ethyl alcohol and diluted acid, is finally dried at 60 DEG C
It is dry.Measure emission spectrum, photoexcitation spectrum, decay of afterglow curve and thermotropic excitation spectrum.
Embodiment 1
The component coefficient of long after glow luminous material is a=0.015, b=0.003, x=0.005.By raw material by chemistry mole
Proportion is weighed and is uniformly mixed, and is placed under air, reducing gas or high pressure inert atmosphere and is calcined, and temperature is 1400~1600 DEG C,
Time is 4h.Firing sample is ground, is then cleaned using deionized water, ethyl alcohol and diluted acid, finally at 60 DEG C
Lower drying.Measure emission spectrum, photoexcitation spectrum, decay of afterglow curve and thermotropic excitation spectrum.
Embodiment 2
The component coefficient of long after glow luminous material is a=0.015, b=0.003, x=0.01.By raw material by chemistry mole
Proportion is weighed and is uniformly mixed, and is placed under air, reducing gas or high pressure inert atmosphere and is calcined, and temperature is 1400~1600 DEG C,
Time is 4h.Firing sample is ground, is then cleaned using deionized water, ethyl alcohol and diluted acid, finally at 60 DEG C
Lower drying.Measure emission spectrum, photoexcitation spectrum, decay of afterglow curve and thermotropic excitation spectrum.
Embodiment 3
The component coefficient of long after glow luminous material is a=0.015, b=0.003, x=0.02.By raw material by chemistry mole
Proportion is weighed and is uniformly mixed, and is placed under air, reducing gas or high pressure inert atmosphere and is calcined, and temperature is 1400~1600 DEG C,
Time is 4h.Firing sample is ground, is then cleaned using deionized water, ethyl alcohol and diluted acid, finally at 60 DEG C
Lower drying.Measure emission spectrum, photoexcitation spectrum, decay of afterglow curve and thermotropic excitation spectrum.
Embodiment 4
The component coefficient of long after glow luminous material is a=0.015, b=0.003, x=0.05.By raw material by chemistry mole
Proportion is weighed and is uniformly mixed, and is placed under air, reducing gas or high pressure inert atmosphere and is calcined, and temperature is 1400~1600 DEG C,
Time is 4h.Firing sample is ground, is then cleaned using deionized water, ethyl alcohol and diluted acid, finally at 60 DEG C
Lower drying.Measure emission spectrum, photoexcitation spectrum, decay of afterglow curve and thermotropic excitation spectrum.
Embodiment 5
The component coefficient of long after glow luminous material is a=0.015, b=0.003, x=0.1.Raw material is matched by chemistry mole
Than weighing and be uniformly mixed, it is placed under air, reducing gas or high pressure inert atmosphere and calcines, temperature is 1400~1600 DEG C, when
Between be 4h.Firing sample is ground, is then cleaned using deionized water, ethyl alcohol and diluted acid, finally at 60 DEG C
Drying.Measure emission spectrum, photoexcitation spectrum, decay of afterglow curve and thermotropic excitation spectrum.
The present invention adjusts the crystallinity of sample and the size of particle by changing the content of boric acid.At the same time, moreover it is possible to
Enough realization long after glow luminous material persistence and sunset glow intensity is adjustable.It can be used for display illumination system of meeting an urgent need, in addition, on
Stating long afterglow can effectively be excited by visible light, this has further expanded its application range.
In order to prove effect of the invention, the decay of afterglow time of all samples is tested, data are listed in Table 1 below.The table is said
Bright long after glow luminous material provided by the present invention has the characteristics that persistence is adjustable.
1 long after glow luminous material afterglow property of table compares
Fig. 1 show powder x-ray diffraction (XRD) figure of the long-afterglow material of all preparations, boric acid or boron oxide plus
Enter to make sample crystallization to enhance.
Show the introducing of boron-containing compound and have not been changed the stable state excitation and transmitting peak position of sample, but defect increases in structure
It is more, lead to sunset glow strength reduction.Its wider excites scope and green-yellow light transmitting range, can satisfy different optical applications
It is required that.
Fig. 3 show the decay of afterglow curve of sample segment, illustrates certain by the regulation of boric acid or oxidation Boron addition
The persistence of long-persistence luminous sample can effectively be changed.
Fig. 4 is the comparison of thermotropic excitation spectrum and photoexcitation spectrum, illustrates to be captured and be used for by defect level sunset glow hair
The luminous energy of light, the activation electronics after light excitation.
Claims (5)
1. a kind of green-yellow light long-afterglow material for improving afterglow property by addition boron, which is characterized in that green-yellow light long afterglow material
The chemical formula of material are as follows:
Y2.982Al2Ga3O12:0.015Ce3+,0.003Yb3+,xH3BO3Wherein 0.003≤a≤0.15,0.0015≤b≤0.15,
0.001≤x≤10%2.
2. the green-yellow light long-afterglow material according to claim 1 for improving afterglow property by addition boron, it is characterised in that
Wherein, 0.05≤x≤0.15,0.03≤y≤0.10.
3. the green-yellow light long-afterglow material according to claim 2 for improving afterglow property by addition boron, it is characterised in that
Wherein x=0.15, y=0.05.
4. a kind of preparation of the green-yellow light long-afterglow material according to claim 1 to 3 for improving afterglow property by addition boron
Method, it is characterised in that include the following steps:
1) general formula Y is pressed3-a-bAl2Ga3O12:aCe3+,bYb3+,xB3+, corresponding raw material in the material is weighed, and be uniformly mixed, set
It is calcined under air, reducing atmosphere or high pressure inert atmosphere, temperature is 1400~1600 DEG C, and the time is 3~6h；
2) the green-yellow light long-afterglow material that step 1) obtains is cleaned using deionized water, ethyl alcohol and diluted acid, is then dried
It is dry.
5. the preparation method of the green-yellow light long-afterglow material according to claim 4 that afterglow property is improved by addition boron,
It is characterized in that oxide of the raw material from yttrium, aluminium, gallium, cerium and ytterbium, boron-based compounds are boric acid or oxidation in step 1)
Boron.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171818A (en) * | 2019-12-25 | 2020-05-19 | 英特美光电（苏州）有限公司 | Preparation method of large-particle aluminum gallate fluorescent powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362465A (en) * | 2000-12-30 | 2002-08-07 | 大连路明发光科技股份有限公司 | New type long-persistence material |
| CN105733580A (en) * | 2016-01-25 | 2016-07-06 | 中国科学院长春应用化学研究所 | Long-afterglow luminescent material and preparation method thereof |
| CN105969355A (en) * | 2016-05-10 | 2016-09-28 | 甘肃稀土新材料股份有限公司 | Yellow-green fluorescent powder and preparation method thereof |
| 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 |
-
2018
- 2018-12-04 CN CN201811472024.1A patent/CN109554178A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1362465A (en) * | 2000-12-30 | 2002-08-07 | 大连路明发光科技股份有限公司 | New type long-persistence material |
| CN105733580A (en) * | 2016-01-25 | 2016-07-06 | 中国科学院长春应用化学研究所 | Long-afterglow luminescent material and preparation method thereof |
| CN105969355A (en) * | 2016-05-10 | 2016-09-28 | 甘肃稀土新材料股份有限公司 | Yellow-green fluorescent powder and preparation method thereof |
| 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 (1)
| Title |
|---|
| YONG-FU LIU等: "A two-step solid-state reaction to synthesize the yellow persistent Gd3Al2Ga3O12:Ce3+ phosphor with an enhanced optical performance for AC-LEDs", 《CHEM. COMMUN.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171818A (en) * | 2019-12-25 | 2020-05-19 | 英特美光电（苏州）有限公司 | Preparation method of large-particle aluminum gallate fluorescent powder |
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Application publication date: 20190402 |