CN109294573A - A kind of matrix near-infrared long lad phosphor and preparation method thereof - Google Patents
A kind of matrix near-infrared long lad phosphor and preparation method thereof Download PDFInfo
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- CN109294573A CN109294573A CN201811328281.8A CN201811328281A CN109294573A CN 109294573 A CN109294573 A CN 109294573A CN 201811328281 A CN201811328281 A CN 201811328281A CN 109294573 A CN109294573 A CN 109294573A
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Abstract
The invention discloses a kind of matrix near-infrared long lad phosphor, luminescent material SrSnO3, replace the 0.5~1.5% of original Sr molar content using Ho.The invention also discloses the preparation methods of matrix near-infrared long lad phosphor comprising following steps: (1) by expression general formula Sr1‑xSnO3:xHo3+, the raw materials of compound containing strontium, stanniferous raw materials of compound and the raw materials of compound containing holmium are weighed respectively；(2) pre-burning in an oxidizing atmosphere after being ground step (1) weighed raw materials of compound；(3) sample after step (2) pre-burning is taken out, calcination in an oxidizing atmosphere after being ground, temperature is 1000 DEG C~1300 DEG C, and the time is 2~7 hours；Obtain matrix near-infrared long lad phosphor.Matrix near-infrared long lad phosphor of the invention, passes through Ho3+Doping, afterglow intensity improve about 8 times, and persistence increases to 32s from 7s.
Description
Technical field
The infrared long-afterglow fluorescent material of the present invention, in particular to a kind of matrix near-infrared long lad phosphor and its preparation side
Method.
Background technique
SrSnO3With perovskite structure (ABO3), because it is in ceramic dielectric body, gas, humidity sensor, lithium ion
The extensive use of cell negative electrode material and photochemical catalyst etc., is increasingly valued by people.Japanese scholars Mizoguchi
Et al. discovery SrSnO3With near-infrared luminous, luminescence band is led in 950nm or so, this wave band in near-infrared bio-imaging etc.
There is potential application value in domain.But there is no literature research SrSnO3Near-infrared it is long-persistence luminous.
Summary of the invention
In order to overcome the disadvantages mentioned above and deficiency of the prior art, the purpose of the present invention is to provide a kind of matrix near-infrared is long
Persistence phosphor passes through Ho3+Doping, afterglow intensity improve about 8 times, and persistence increases to 32s from 7s.
Another object of the present invention is to provide a kind of preparation methods of matrix near-infrared long lad phosphor.
The purpose of the present invention is achieved through the following technical solutions:
A kind of matrix near-infrared long lad phosphor, luminescent material SrSnO3, original Sr molar content is replaced using Ho
0.5~1.5%.
X=0.010.
A kind of preparation method of matrix near-infrared long lad phosphor, comprising the following steps:
(1) by expression general formula Sr1-xSnO3:xHo3+, the raw materials of compound containing strontium, stanniferous raw materials of compound are weighed respectively
And the raw materials of compound containing holmium；Wherein elemental mole ratios are Sr:O:Sn:Ho=1-x:3:1:x, wherein 0.5≤x < 1.5%；Ho
The Sr in crystal, x is replaced to indicate Replacement rate；
(2) pre-burning in an oxidizing atmosphere after being ground step (1) weighed raw materials of compound；
(3) sample after step (2) pre-burning is taken out, calcination in an oxidizing atmosphere after being ground, temperature 1000
DEG C~1300 DEG C, the time is 2~7 hours；Obtain matrix near-infrared long lad phosphor.
Step (2) described pre-burning, specifically: calcined temperature is 600~800 DEG C, and the time is 2~6 hours.
Step (2) oxidizing atmosphere is air atmosphere or oxygen atmosphere.
The raw materials of compound containing strontium is any one in strontium carbonate, strontium oxide strontia and strontium hydroxide.
The stanniferous raw materials of compound is tin oxide, any one in stannous oxide.
The raw materials of compound containing holmium is holimium oxide.
When T=1200 DEG C, t=4h, illumination effect is best at this time.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) matrix near-infrared long lad phosphor of the invention, passes through Ho3+Doping, it is remaining by about 8 times of afterglow intensity raising
The brightness time increases to 32s from 7s.
(2) preparation condition of the invention is simple, at low cost using high temperature solid-state method, is convenient for volume production.
(3) matrix near-infrared long lad phosphor of the invention, which is hoped, realizes application in fields such as bio-imagings.
Detailed description of the invention
Fig. 1 is the powder x-ray diffraction spectrum of proportion (1) sample of embodiment 1.
Fig. 2 is the twilight sunset spectrum of proportion (3) sample of embodiment 1.
Fig. 3 is the integral curve that the afterglow intensity of proportion (3) sample of embodiment 1 changes over time.
Fig. 4 is the twilight sunset spectrum of proportion (1) sample of embodiment 1.
Fig. 5 is the integral curve that the afterglow intensity of the proportion (1) of embodiment 1 changes over time.
The twilight sunset spectrum of proportion (3) and (1) of embodiment 1 when Fig. 6 is 1s.
The integrated intensity comparison of the twilight sunset spectrum of the twilight sunset and matrix of the proportion (3) and (1) of embodiment 1 when Fig. 7 is 1s
Figure.
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
It chooses strontium carbonate, stannic oxide, holimium oxide and makees initial compounds raw material, by each element mol ratio, weigh 3 respectively
Kind raw materials of compound, matches as follows totally by 4 groups:
(1) Sr:Sn:Ho=1.000:1.000:0.000, corresponding x=0.000；
(2) Sr:Sn:Ho=0.995:1.000:0.005, corresponding x=0.005；
(3) Sr:Sn:Ho=0.990:1.000:0.010, corresponding x=0.010；
(4) Sr:Sn:Ho=0.985:1.000:0.015, corresponding x=0.015；
After the ground mixing of mixture, it is put into corundum crucible, crucible is then put into high-temperature electric resistance furnace.Accurate control heating speed
Rate, sample 800 DEG C pre-burning 2 hours.Sample after pre-burning is taken out, after regrinding mixes, is put into crucible, under air
1200 DEG C calcination 4 hours, with furnace natural cooling to get to holmium doping stannic acid base status near-infrared long lad phosphor.
Fig. 1 is the powder x-ray diffraction spectrum of proportion (1) sample of the present embodiment, and spectral line uses Japan Rigaku D/
The measurement of max-IIIA X-ray diffractometer, test voltage 40kV, 1.2 °/min of scanning speed test electric current 40mA, select Cu-K α
1X ray, wavelength areX-ray diffraction analysis shows that matching (1) is SrSnO3Phase belongs to cubic system, PmSpace group.
Fig. 2 is the twilight sunset spectrum of proportion (3) sample of the present embodiment.Using U.S. marine optics QE650pro, optical fiber is straight
Diameter is 600 μm, time of integration 800ms, and can survey wavelength is 300~1000nm, excitation wavelength 254nm, and firing time is
30s.As shown in Figure 2, sample is under 254nm ultraviolet excitation with the near-infrared long afterglow of 800-100nm.Wherein there are two shoulders
Peak is located at 924nm and 968nm.
Fig. 3 is the integral curve that the afterglow intensity of proportion (3) sample of the present embodiment changes over time.From the figure 3, it may be seen that sample
Product afterglow intensity has a rapid decay within the 5s most started, and the rate of decay slows down between 5-30s, persistence about 32s.
Fig. 4 is the twilight sunset spectrum of proportion (1) sample of the present embodiment.Instrument and the same Fig. 2 of test condition.By Fig. 4
It is found that sample is under 254nm ultraviolet excitation with the near-infrared long afterglow of 800-100nm.Wherein there are two acromions to distinguish position
In 924nm and 968nm.Illustrate that the luminous of this system is shining for matrix itself.
Fig. 5 is the integral curve that the afterglow intensity of the proportion (1) of embodiment 1 changes over time.As shown in Figure 4, sample
There are a rough negative correlativing relation, persistence about 7s in decay of afterglow and time within the 5s most started.
The twilight sunset spectrum of proportion (3) and (1) of embodiment 1 when Fig. 6 is 1s.As shown in Figure 5, matrix and the twilight sunset for mixing Ho
Peak position is consistent, is located at 924nm and 968nm there are two acromion, illustrates the twilight sunset from matrix itself.But doping Ho with
Afterwards, afterglow intensity is remarkably reinforced.
The integrated intensity comparison of the twilight sunset spectrum of the twilight sunset and matrix of the proportion (3) and (1) of embodiment 1 when Fig. 7 is 1s
Figure.It will be appreciated from fig. 6 that the afterglow intensity of matrix increases to 6748.17 from 857.77, increases 8 times after doping.
Embodiment 2
It chooses strontium oxide strontia, stannic oxide, holimium oxide and makees initial compounds raw material, by each element mol ratio Sr:Sn:Ho=
0.990:1.000:0.010, corresponding x=0.010；Three kinds of raw materials are weighed respectively is put into corundum earthenware after the ground mixing of mixture
Then crucible is put into high-temperature electric resistance furnace by crucible.Sample 800 DEG C pre-burning 2 hours.Sample after pre-burning is taken out, regrinding is mixed
After even, at temperature T (T=1000,1100,1200,1300) calcination 4 hours under air, adulterated with furnace natural cooling to get to holmium
Stannic acid base status near-infrared long lad phosphor.X-ray diffraction analysis shows it for SrSnO3Crystal phase.The spectrum of fluorescent powder
Property is similar with (3) are matched in embodiment 1, shines at T=1200 DEG C most strong.
Embodiment 3
It chooses strontium oxide strontia, stannous oxide, holimium oxide and makees initial compounds raw material, by each element mol ratio Sr:Sn:Ho=
0.990:1.000:0.010, corresponding x=0.010；Three kinds of raw materials are weighed respectively is put into corundum earthenware after the ground mixing of mixture
Then crucible is put into high-temperature electric resistance furnace by crucible.Sample 800 DEG C pre-burning 2 hours.Sample after pre-burning is taken out, regrinding is mixed
After even, at temperature T (T=1000,1100,1200,1300) calcination 4 hours under air, adulterated with furnace natural cooling to get to holmium
Stannic acid base status near-infrared long lad phosphor.X-ray diffraction analysis shows it for SrSnO3Crystal phase.The spectrum of fluorescent powder
Property is similar with (3) are matched in embodiment 1, shines at T=1200 DEG C most strong.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (9)
1. a kind of matrix near-infrared long lad phosphor, which is characterized in that luminescent material SrSnO3, replace original Sr to rub using Ho
The 0.5~1.5% of that content.
2. matrix near-infrared long lad phosphor according to claim 1, which is characterized in that x=0.010.
3. a kind of preparation method of matrix near-infrared long lad phosphor, which comprises the following steps:
(1) by expression general formula Sr1-xSnO3:xHo3+, the raw materials of compound containing strontium, stanniferous raw materials of compound are weighed respectively and are contained
The raw materials of compound of holmium；Wherein elemental mole ratios are Sr:O:Sn:Ho=1-x:3:1:x, wherein 0.5≤x < 1.5%；Ho replaces
Sr in crystal, x indicate Replacement rate；
(2) pre-burning in an oxidizing atmosphere after being ground step (1) weighed raw materials of compound；
(3) by after step (2) pre-burning sample take out, calcination in an oxidizing atmosphere after being ground, temperature be 1000 DEG C~
1300 DEG C, the time is 2~7 hours；Obtain matrix near-infrared long lad phosphor.
4. the preparation method of matrix near-infrared long lad phosphor according to claim 3, which is characterized in that step (2)
The pre-burning, specifically: calcined temperature is 600~800 DEG C, and the time is 2~6 hours.
5. the preparation method of matrix near-infrared long lad phosphor according to claim 3, which is characterized in that step (2)
The oxidizing atmosphere is air atmosphere or oxygen atmosphere.
6. the preparation method of matrix near-infrared long lad phosphor according to claim 3, which is characterized in that described to contain strontium
Raw materials of compound be strontium carbonate, strontium oxide strontia and strontium hydroxide in any one.
7. the preparation method of matrix near-infrared long lad phosphor according to claim 3, which is characterized in that described stanniferous
Raw materials of compound be tin oxide, any one in stannous oxide.
8. the preparation method of matrix near-infrared long lad phosphor according to claim 3, which is characterized in that described to contain holmium
Raw materials of compound be holimium oxide.
9. the preparation method of matrix near-infrared long lad phosphor according to claim 3, which is characterized in that T=1200
DEG C, t=4h.
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| CN106433641A (en) * | 2016-09-05 | 2017-02-22 | 中南大学 | Method for preparing rare earth doped calcium stannate fluorescent material through low-temperature solid-phase reaction method |
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Application publication date: 20190201 |