CN104342154A - Lead difluoride base material with Eu<2+> characteristic luminescence and preparation method thereof - Google Patents
Lead difluoride base material with Eu<2+> characteristic luminescence and preparation method thereof Download PDFInfo
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- CN104342154A CN104342154A CN201310347814.8A CN201310347814A CN104342154A CN 104342154 A CN104342154 A CN 104342154A CN 201310347814 A CN201310347814 A CN 201310347814A CN 104342154 A CN104342154 A CN 104342154A
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Abstract
The invention relates to a lead difluoride base material with Eu<2+> characteristic luminescence and a preparation method thereof. The chemical structure general formula of the base material is Pb1-x (Ca1-yEuy)xF2, wherein y is not less than 0.005 and not greater than 0.05 and x is not less than 0.05. The base material is prepared through codoping thermal treatment by taking PbF2 as a matrix and Ca1-yEuy as a codoping agent, wherein the codoping agent is prepared through thermal treatment with the temperature of 800-900 DEG C by taking CaF2 as a matrix and EuF2 or EuF3 as a doping agent. In the base material disclosed by the invention, Eu mainly exists in a form of Eu<2+> so that Eu<2+> characteristic luminescence (5d-4f transition) with a band spectrum and high attenuation speed is combined with an excellent Cherenkov luminophor (PbF2) with high density and relatively low price. Therefore, the lead difluoride base material with Eu<2+> characteristic luminescence can be applied to research of a PbF2-based double readable material (crystal/glass/ceramic) and has an important practical value in the research and application field of high energy physics.
Description
Technical field
The present invention relates to a kind of luminescent material, be specifically related to one and there is divalent europium (Eu
2+) PbF of characteristic luminescence
2base powder body material and preparation method thereof, belongs to the technical field of inorganic fluorescent material, scintillation material.
Background technology
Highdensity scintillation material is the core material in high-energy particle physics experimental detection device, most of scintillation material has good energy resolution for incident electron or photon, and it is lower for the resolving power of the larger high energy particle (as hadron) of other e/h ratio, detection performance is poor, therefore, exploitation can detect the scintillation material of electronics, photon and more high energy particle is simultaneously a science and technology challenge.
Along with the continuous exploration that people originate to material, can by twinkling light (visible light wave range) and Cherenkov(Cherenkov in the urgent need to one in high-energy physics experiment, ultraviolet band) light read simultaneously two read the core material of material (DREAM) as detector of new generation (homogeneous hadron calorimeter (HHCAL)), in order to express motion and the energy state of low energy particle and high energy particle simultaneously.Here, when the Cherenkov mentioned only refers to that high energy particle passes transparent medium, when velocity of particle is higher than the luminescence phenomenon produced during light velocity of propagation in media as well, be usually used in detecting high energy particle (as hadron).
At present, the potential candidate of two reading material has PbF
2, PbFCl, Bi
4si
3o
12(BSO), Bi
4ge
3o
12(BGO), PbWO
4(PWO).Wherein PbF
2crystal is a kind of Cherenkov twinkler of excellence, not only high (the 7.7g/cm of density
3), ultraviolet absorption edge short (240nm), and cheap comparatively speaking, but through the effort of nearly 20 years, up to now not yet at PbF
2twinkling light available under introducing room temperature in matrix.The people such as Mao (IEEE Transactions on Nuclear Science, 57 (6) (2010), 3841-3845) are once to nearly 116 rare earth ion doped PbF
2sample is studied, although find that these samples can launch visible ray, their fall time is too slow, all in millisecond magnitude, such as mixes the PbF of trivalent Eu
2the fall time of sample is 8.5ms, can not meet two technical indicator reading material.
The PbF mixing Eu of people's researchs such as above-mentioned Mao
2eu in sample is with Eu
3+form exist, Eu
3+luminescence results from f-f transition, and according to Fermic golden rule, fall time of light that f-f transition is launched is usually long, and the fall time of the sample measured as people such as Mao is in ms magnitude.Eu
2+ion is one more stable in bivalent rare earth ion, Eu
2+light sources in 5d-4f transition, the light that 5d-4f transition is launched normally is decayed soon, but due to PbF
2strong oxidizing property, Eu usually can with high price Eu
3+form be present in PbF
2in, the 50GeO mixing Eu prepared by the people (Optical Materials, 33 (2011), 791-798) such as such as C.Bensalem
2-40PbO-10PbF
2glass-ceramic, PbF
2the PbO-PbF mixing Eu prepared by the people such as polycrystalline ceramics and PNachimuthu (Proceeding of the Indian Academy of Sciences (Chemical Sciences), 107 (1) (1995), 59-66)
2eu in glass is all with Eu
3+form exist.In fluoride materials, CaF
2that one well can obtain Eu
2+matrix, Eu is at CaF
2in have Eu
2+form exist (Optical Materials, 33 (2011), 735-737), its fall time is 940ns, luminous zone main peak is positioned at 435nm(Saint-Gobain Crystals), relatively be applicable to effectively being separated with Cherenkov light (ultraviolet), therefore, the mode of mixing altogether with Ca, Eu is likely at PbF
2eu is obtained in sill
2+characteristic luminescence.
Summary of the invention
One is the object of the present invention is to provide to have Eu
2+the PbF of characteristic luminescence
2base powder body material and preparation method thereof, thus having the Eu of band spectrum, fast decay
2+characteristic luminescence (5d-4f transition) and high-density, relative low price Cherenkov twinkler---the PbF of excellence
2combine.
At this, on the one hand, the invention provides one and there is Eu
2+the PbF of characteristic luminescence
2base powder body material, the chemical constitution general formula of described material is Pb
1-x(Ca
1-yeu
y)
xf
2, wherein 0.005≤y≤0.05, x>=0.05, described material is with PbF
2for matrix, with Ca
1-yeu
yfor co-dopant obtains through codoped thermal treatment, described co-dopant Ca
1-yeu
ywith CaF
2for matrix, EuF
2or EuF
3for doping agent thermal treatment at 800 ~ 900 DEG C obtains.
In described material of the present invention, Eu is mainly with Eu
2+form exists, thus having the Eu of band spectrum, fast decay
2+characteristic luminescence (5d-4f transition) and high-density, relative low price Cherenkov twinkler---the PbF of excellence
2combine, can be used for PbF
2the two development reading material (crystal/glass/ceramic) of base, has important practical to be worth in study of high energy physics and Application Areas.
In the present invention, when the heat treated temperature of described codoped is greater than PbF
2fusing point time, preferably, x>=0.2.
In the present invention, preferably, y=0.03.
Eu in described material
2+characteristic luminescence and Eu
3+the strength ratio of characteristic luminescence is (2 ~ 110): 1.Such as, Pb
1- x(Ca
0.995eu
0.005)
xf
2(550) Eu in
2+characteristic luminescence (near peak value 422nm, 390 ~ 500nm) and Eu
3+the ratio of the integrated intensity of characteristic luminescence (multiple narrow peak, 550 ~ 750nm) is 7.8:1 (x=5%), 14.1:1 (x=10%), 25.7:1 (x=15%), Pb
1-x(Ca
0.995eu
0.005)
xf
2(900) Eu in
2+and Eu
3+the ratio of characteristic luminescence integrated intensity be 2.2:1 (x=20%), 3.9:1 (x=25%), 7.6:1 (x=30%).
In the present invention, described Eu
2+characteristic luminescence be at 320 ~ 400nm(peak value near 336nm) 390 ~ 500nm(peak value of producing under optical excitation is near 422nm) and characteristic luminescence band.
On the other hand, the invention provides and a kind of above-mentioned there is Eu
2+the PbF of characteristic luminescence
2the preparation method of base powder body material, described method comprises:
(1) with CaF
2for matrix, EuF
2or EuF
3for doping agent, by after stoicheiometry mixed grinding in 800 ~ 900 DEG C under protection of inert gas thermal treatment obtain co-dopant (Ca
1-yeu
y) F
2; And
(2) with PbF
2for matrix, with (Ca
1-yeu
y) F
2for co-dopant, after stoicheiometry mixed grinding, described in obtained through codoped thermal treatment under protection of inert gas and under the existence of reductor, there is Eu
2+the PbF of characteristic luminescence
2sill.
In the present invention, the heat treated temperature of described codoped is not by described PbF
2the restriction of the fusing point of matrix, namely all can prepare at higher or lower than the temperature of its fusing point and have Eu
2+the PbF of characteristic luminescence
2base powder body material, and the present invention can be realized by simple two step doping, technique is simple, applied widely.
Preferably, in described step (1), the heat treated time can be 1 ~ 2 hour.
Preferably, in described step (2), the heat treated temperature of described codoped can be 500 ~ 1000 DEG C, and the time can be 0.5 ~ 3 hour.
In a preferred example, the heat treated temperature of described codoped is higher than PbF
2fusing point (824 DEG C), (Ca
1-yeu
y) F
2with PbF
2mol ratio be preferably more than 1/4.
In another preferred example, the heat treated temperature of described codoped is lower than PbF
2fusing point (824 DEG C), (Ca
1-yeu
y) F
2with PbF
2mol ratio be preferably more than 1/19.
Preferably, described reductor can be tetrafluoroethylene.
Accompanying drawing explanation
Fig. 1 (a) ~ Fig. 1 (d) is with CaF
2, EuF
2for raw material, the Ca prepared under 700 DEG C, 800 DEG C, 900 DEG C, 1000 DEG C thermal treatment temps respectively
0.995eu
0.005f
2(700) (Fig. 1 (a)), Ca
0.995eu
0.005f
2(800) (Fig. 1 (b)), Ca
0.995eu
0.005f
2(900) (Fig. 1 (c)), Ca
0.995eu
0.005f
2(1000) the exciting and emmission spectrum of (Fig. 1 (d)) serial powder sample, Fig. 1 (e) is Ca
0.995eu
0.005f
2(900) sample and Eu
3+what characteristic luminescence was relevant excites (emission wavelength 591nm) and launches the enlarged view of (excitation wavelength 392nm) spectrum;
Fig. 2 (a), Fig. 2 (b) are respectively with CaF
2, EuF
3for raw material, the Ca prepared under 800 DEG C, 900 DEG C thermal treatment temps respectively
0.995eu
0.005f
2(800-EuF
3) (Fig. 2 (a)), Ca
0.995eu
0.005f
2(900-EuF
3) (exciting and emmission spectrum of Fig. 2 (b) powder sample;
The Ca that Fig. 3 (a) is different levels of doping
1-xeu
xf
2the emmission spectrum of (x=0,0.1%, 0.3%) powder sample under the optical excitation of 336nm wavelength, shows typical Eu
3+characteristic luminescence;
The Ca that Fig. 3 (b) is different levels of doping
1-xeu
xf
2exciting (emission wavelength 423/425nm) and launching (excitation wavelength 336nm) spectrum of (x=1%, 3%, 5%) powder sample, shows typical Eu
2+characteristic luminescence;
Fig. 4 (a) is Pb
1-x(Ca
0.995eu
0.005)
xf
2(900) the exciting of (x=0,5%, 10%, 20%, 25%, 30%) serial powder sample (emission wavelength 421nm) and launch (excitation wavelength 337nm) spectrum, shows typical Eu
2+characteristic luminescence, the thermal treatment temp of this series of samples is 900 DEG C;
Fig. 4 (b) is Pb
1-x(Ca
0.995eu
0.005)
xf
2(900) the exciting of (x=0,5%, 10%, 20%, 25%, 30%) serial powder sample (emission wavelength 591/590nm) and launch (excitation wavelength 392nm) spectrum, shows typical Eu
3+characteristic luminescence, the thermal treatment temp of this series of samples is 900 DEG C;
Fig. 5 (a) is Pb
0.8ca
0.199eu
0.001f
2(550) emmission spectrum of powder sample respectively under 336 and 392nm wavelength excite and launch monitor wavelength be 422 and 591nm under excitation spectrum, Fig. 5 (b) is Pb
0.8ca
0.199eu
0.001f
2and Eu (550)
3+what characteristic luminescence was relevant excites (emission wavelength 591nm) and launches the enlarged view of (excitation wavelength 392nm) spectrum, and the thermal treatment temp of this sample is 550 DEG C;
Fig. 6 (a) is Pb
1-x(Ca
0.995eu
0.005)
xf
2(550) the exciting of (x=0,1%, 5%, 10%, 15%) serial powder sample (emission wavelength 422nm) and launch (excitation wavelength 336nm) spectrum, shows typical Eu
2+characteristic luminescence, the thermal treatment temp of this series of samples is 550 DEG C;
Fig. 6 (b) is Pb
1-x(Ca
0.995eu
0.005)
xf
2(550) the exciting of (x=0,1%, 5%, 10%, 15%) serial powder sample (emission wavelength 591nm) and launch (excitation wavelength 392nm) spectrum, shows typical Eu
3+characteristic luminescence, the thermal treatment temp of this series of samples is 550 DEG C.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment is only for illustration of the present invention, and unrestricted the present invention.
One is the object of the present invention is to provide to have Eu
2+the PbF of characteristic luminescence
2base powder body material and preparation method thereof, thus having the Eu of band spectrum, fast decay
2+characteristic luminescence (5d-4f transition) and high-density, relative low price Cherenkov twinkler---the PbF of excellence
2combine, this design of material thought and technology of preparing can be used for PbF
2the two development reading material (crystal/glass/ceramic) of base, will have very important practical value in study of high energy physics and Application Areas.
Of the present invention have Eu
2+the PbF of characteristic luminescence
2the chemical constitution general formula of base powder body material is Pb
1-x(Ca
1-yeu
y)
xf
2, wherein 0.005≤y≤0.05, x>=0.05, described material is with PbF
2for matrix, with Ca
1-yeu
yfor co-dopant obtains through codoped thermal treatment, described co-dopant Ca
1-yeu
ywith CaF
2for matrix, EuF
2or EuF
3for doping agent thermal treatment at 800 ~ 900 DEG C obtains.When the heat treated temperature of described codoped is greater than PbF
2fusing point time, preferably, x>=0.2.Preferably, y=0.03.Eu in described material
2+characteristic luminescence and Eu
3+the strength ratio of characteristic luminescence can be (2 ~ 110): 1.Such as, as y=0.005, Pb
1-x(Ca
0.995eu
0.005)
xf
2(550) Eu in
2+characteristic luminescence (near peak value 422nm, 390 ~ 500nm) and Eu
3+the ratio of the integrated intensity of characteristic luminescence (multiple narrow peak, 550 ~ 750nm) is 7.8:1 (x=5%), 14.1:1 (x=10%), 25.7:1 (x=15%), Pb
1-x(Ca
0.995eu
0.005)
xf
2(900) Eu in
2+and Eu
3+the ratio of characteristic luminescence integrated intensity be 2.2:1 (x=20%), 3.9:1 (x=25%), 7.6:1 (x=30%).
Of the present invention have Eu
2+the PbF of characteristic luminescence
2the preparation method of base powder body material comprises:
(1) with CaF
2for matrix, EuF
2or EuF
3for doping agent, by after stoicheiometry mixed grinding in 800 ~ 900 DEG C under protection of inert gas thermal treatment obtain co-dopant (Ca
1-yeu
y) F
2; And
(2) with PbF
2for matrix, with (Ca
1-yeu
y) F
2for co-dopant, after stoicheiometry mixed grinding, described in obtained through codoped thermal treatment under protection of inert gas and under the existence of reductor, there is Eu
2+the PbF of characteristic luminescence
2sill.
Particularly, exemplarily, the present invention can comprise the following steps.
First with EuF
2or EuF
3for doping agent, with CaF
2matrix is by required stoicheiometry mixed grinding, and in heating installation such as box-type furnace, 800 ~ 900 DEG C of insulations 1 ~ 2 hour under inert atmosphere, prepare (Ca
1-yeu
y) F
2middle powder, wherein a mole doping content of Eu can be 0.5%≤y≤5%.
Then with (Ca
1-yeu
y) F
2middle powder is doping agent, PbF
2for matrix, by required stoicheiometry mixed grinding, finally add reductor, heat-treat under inert atmosphere in heating installation such as box-type furnace.Wherein said reductor includes but not limited to ptfe micropowder (PTFE).Again, the add-on of described reductor is for preventing (Ca
1-yeu
y) F
2and PbF
2oxidized amount.In addition, described heat treated temperature can be 500 ~ 1000 DEG C, and the time can be 0.5 ~ 3 hour.
Middle powder (Ca
1-yeu
y) F
2doping content can select according to described heat treated treatment temp.When thermal treatment temp is higher than PbF
2fusing point---when 824 DEG C, preferably Ca
0.995eu
0.005f
2mole doped parameterx>=20%, thus obtain stronger Eu
2+luminous.When thermal treatment temp is lower than PbF
2fusing point---when 824 DEG C, preferably Ca
0.995eu
0.005f
2mole doped parameterx>=5%, thus obtain stronger Eu
2+luminous.
The mode of therefore mixing altogether with Ca, Eu can be prepared has Eu
2+the PbF of characteristic luminescence
2original washing powder body, in addition, though be thermal treatment temp higher than or lower than PbF
2fusing point, can Eu be obtained
2+characteristic luminescence, this illustrates and adopts this design of material thought and preparation method to be hopeful to prepare PbF
2the bulk materials such as base glass, glass-ceramic, crystalline ceramics or crystal, thus reach two application requiring reading material, and then be generalized to other Application Areas of luminescent material.
Embodiment of illustrating further is below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; and limiting the scope of the invention can not be interpreted as, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The temperature of reaction that following example is concrete, time etc. are also only examples in OK range, and namely, those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
With CaF
2, EuF
2for raw material, under the thermal treatment temp of 700,800,900,1000 DEG C, prepare Ca respectively
0.995eu
0.005f
2(700), Ca
0.995eu
0.005f
2(800), Ca
0.995eu
0.005f
2(900), Ca
0.995eu
0.005f
2(1000) series of samples.
With CaF
2, EuF
2for raw material, fixation of C aF
2with EuF
2mol ratio be 0.995:0.005, preparation raw material mixed grinding, under in box-type furnace, Ar atmosphere encloses protection respectively, 700,800,900,1000 DEG C of insulations are heat-treated for 1 ~ 2 hour, and furnace cooling, prepares Ca
0.995eu
0.005f
2(700), Ca
0.995eu
0.005f
2(800), Ca
0.995eu
0.005f
2(900), Ca
0.995eu
0.005f
2(1000) series of samples.
As shown in Fig. 1 (a), the sample Ca of 700 DEG C of process
0.995eu
0.005f
2(700) in mainly 393nm wavelength optical excitation under derive from Eu at 613nm place
3+'s
5d
0→
7f
2the luminescence of transition, under the optical excitation of 336nm wavelength, has at 422nm place and more weak derives from Eu
2+4f
65d
1→ 4f
7the luminous zone of transition, Eu
2+and Eu
3+the ratio of characteristic luminescence integrated intensity be 0.9:1; Along with the rising for the treatment of temp, as shown in Fig. 1 (b), 1 (c), the sample Ca of 800,900 DEG C of process
0.995eu
0.005f
2(800), Ca
0.995eu
0.005f
2(900) in, mainly 336nm wavelength light excites down and derives from Eu at 422/424nm place
2+4f
65d
1→ 4f
7the luminous zone of transition, and Ca
0.995eu
0.005f
2(900) luminous intensity is far away higher than Ca
0.995eu
0.005f
2(800), under the optical excitation of 392nm wavelength, Ca
0.995eu
0.005f
2(800) in 592,612nm place derives from Eu
3+'s
5d
0→
7f
1,
5d
0→
7f
2transition and Ca
0.995eu
0.005f
2(900) in, 591nm place derives from Eu
3+'s
5d
0→
7f
1the luminescence of transition is all very weak, Ca
0.995eu
0.005f
2(800), Ca
0.995eu
0.
005f
2(900) Eu in
2+and Eu
3+the ratio of characteristic luminescence integrated intensity be respectively 24.3:1,654.9:1; As shown in Fig. 1 (d), the sample Ca of 1000 DEG C of process
0.995eu
0.005f
2(1000) under the optical excitation of 336nm wavelength, the Eu near 422nm is not substantially had
2+luminescence, derive from Eu at 574nm place under the optical excitation of mainly 459nm wavelength
3+'s
5d
1→
7f
2the luminescence of transition.
With CaF
2, EuF
2for raw material, can obtain stronger there is Eu under the thermal treatment temp of 800 ~ 900 DEG C
2+the Ca of characteristic luminescence
0.995eu
0.005f
2, and the sample Ca of 900 DEG C of process
0.995eu
0.005f
2(900) luminous intensity is higher than the sample Ca of 800 DEG C of process
0.995eu
0.005f
2(800).
Embodiment 2
With CaF
2, EuF
3for raw material, under the thermal treatment temp of 800,900 DEG C, prepare Ca respectively
0.995eu
0.005f
2(800-EuF
3), Ca
0.995eu
0.005f
2(900-EuF
3) sample, mainly study with EuF
3for raw material could obtain Eu
2+luminescence.
With CaF
2, EuF
3for raw material, fixation of C aF
2with EuF
3mol ratio be 0.995:0.005, preparation raw material mixed grinding, under in box-type furnace, Ar atmosphere encloses protection respectively, 800,900 DEG C of insulations are heat-treated for 1 ~ 2 hour, and furnace cooling, prepares Ca
0.995eu
0.005f
2(800-EuF
3), Ca
0.995eu
0.005f
2(900-EuF
3) sample.
As shown in Fig. 2 (a), 2 (b), due to charge compensation principle, sample Ca
0.995eu
0.005f
2(800-EuF
3) and Ca
0.995eu
0.005f
2(900-EuF
3) in all mainly 336nm wavelength optical excitation under derive from Eu at 422nm place
2+4f
65d
1→ 4f
7the luminous zone of transition, also has simultaneously and derives from Eu at 592nm place under the optical excitation of 392nm wavelength
3+'s
5d
0→
7f
1the luminescence of transition, Ca
0.995eu
0.005f
2(800-EuF
3), Ca
0.995eu
0.005f
2(900-EuF
3) middle Eu
2+and Eu
3+the ratio of characteristic luminescence integrated intensity be respectively 18.8:1,5.3:1, interpret sample Ca
0.995eu
0.005f
2(800-EuF
3) middle Eu
2+content higher than sample Ca
0.995eu
0.005f
2(900-EuF
3).
With CaF
2, EuF
3for raw material, under the thermal treatment temp of 800 ~ 900 DEG C, also can obtain stronger there is Eu
2+the Ca of characteristic luminescence
0.995eu
0.005f
2.
Embodiment 3
With CaF
2, EuF
2for raw material, under the thermal treatment temp of 900 DEG C, prepare the Ca of serial different levels of doping
1-xeu
xf
2(x=0,0.1%, 0.3%, 1%, 3%, 5%) sample.
With CaF
2, EuF
2for raw material, by CaF
2with EuF
2mol ratio be (1-x): x (x=0,0.1%, 0.3%, 1%, 3%, 5%) mixed grinding, under in box-type furnace, Ar atmosphere encloses protection, 900 DEG C of insulations are heat-treated for 2 hours, and furnace cooling, prepares series of samples Ca
1-xeu
xf
2(x=0,0.1%, 0.3%, 1%, 3%, 5%).
As shown in Fig. 3 (a), when doped parameterx is 0.1%, 0.3%, under the optical excitation of 336nm wavelength, Ca
1- xeu
xf
2in (x=0.1%, 0.3%) sample mainly 574nm place derive from Eu
3+'s
5d
1→
7f
2the luminescence of transition, basic derives from Eu not near 422nm
2+luminous zone, Ca
1-xeu
xf
2eu in (x=0.1%, 0.3%) sample is mainly with Eu
3+form exist; As shown in Fig. 3 (b), when doped parameterx is 1%, 3%, when 5%, under the optical excitation of 336nm wavelength, Ca
1-xeu
xf
2eu is derived from (x=1%, 3%, 5%) sample mainly near 423/425nm
2+4f
65d
1→ 4f
7the luminous zone of transition, when doped parameterx=3%, luminous intensity is the strongest, and due to concentration quenching effect, doping content increases further, and when doped parameterx=5%, luminous intensity slightly declines, Ca
1-xeu
xf
2eu in (x=1%, 3%, 5%) sample is mainly with Eu
2+form exist.
Embodiment 4
At 900 DEG C (higher than PbF
2fusing point---824 DEG C) thermal treatment temp under prepare Pb
1-x(Ca
0.995eu
0.005)
xf
2(900) (x=0,5%, 10%, 20%, 25%, 30%) series of samples.
First with CaF
2, EuF
2for raw material, fixation of C aF
2with EuF
2mol ratio be 0.995:0.005, preparation raw material mixed grinding, under in box-type furnace, Ar atmosphere encloses protection, 900 DEG C of insulations are heat-treated for 2 hours, and furnace cooling, prepares Ca
0.995eu
0.005f
2middle powder;
Then with PbF
2and Ca
0.995eu
0.005f
2for raw material, by PbF
2with Ca
0.995eu
0.005f
2mol ratio be (1-x): x preparation raw material, mixed grinding, adds PTFE reductor;
Finally in box-type furnace, Ar atmosphere is incubated 30 minutes in 900 DEG C under enclosing protection, and furnace cooling, prepares serial powder sample Pb
1-x(Ca
0.995eu
0.005)
xf
2(900) (x=0,5%, 10%, 20%, 25%, 30%).
As shown in Fig. 4 (a), under the optical excitation of 337nm wavelength, work as Ca
0.995eu
0.005f
2mole doped parameterx=5% time, Pb
1-x(Ca
0.995eu
0.005)
xf
2(900) sample does not have luminescence substantially, and as x=10%, sample has very weak luminescence near 421nm, when x>=20%, sample has stronger luminous zone near 421nm, and along with the further increase of doping content, the luminous intensity of sample strengthens thereupon.The luminous zone at 421nm place is Eu
2+characteristic emission, come from excited state 4f
65d
1to ground state 4f
7transition.As shown in Fig. 4 (b), when under the optical excitation at 392nm wavelength, Pb
1- x(Ca
0.995eu
0.005)
xf
2(900) sample 511,555,590,615,700nm place launches more weak glow peak, corresponds respectively to Eu
3+'s
5d
2→
7f
3,
5d
1→
7f
1,
5d
0→
7f
1,
5d
0→
7f
2,
5d
0→
7f
4transition, along with Ca
0.995eu
0.005f
2the increase of doping content, Eu
3+glow peak intensity have enhancing to a certain degree, but still very weak.In addition, under the optical excitation of 392nm wavelength, Pb
1-x(Ca
0.995eu
0.005)
xf
2(900) there is stronger glow peak equally in sample near 419nm, comes from Eu
2+4f
65d
1→ 4f
7transition because the launch monitor wavelength in Fig. 4 (a) be the wavelength region that the excitation spectrum under 421nm contains wider (about 320 ~ 400nm), so excite lower sample can launch the Eu at the 419nm place in Fig. 4 (b) at 392nm
2+4f
65d
1→ 4f
7the light of transition.Pb
1-x(Ca
0.995eu
0.005)
xf
2(900) Eu in sample
2+and Eu
3+the ratio of characteristic luminescence integrated intensity be 2.2:1 (x=20%), 3.9:1 (x=25%), 7.6:1 (x=30%), Pb
1- x(Ca
0.995eu
0.005)
xf
2(900) in (x>=20%) sample, most of Eu ion is with Eu
2+form exist, seldom a part is with Eu
3+form exist.
Embodiment 5
At 550 DEG C (lower than PbF
2fusing point---824 DEG C) thermal treatment temp under prepare Pb
0.8ca
0.199eu
0.001f
2(550) sample (Pb in composition and embodiment 4
1-x(Ca
0.995eu
0.005)
xf
2(900) (x=20%), i.e. Pb
0.8ca
0.199eu
0.001f
2(900) identical), so that determine whether can lower than PbF
2at PbF under the thermal treatment temp of fusing point
2eu is obtained in sill
2+characteristic luminescence.
First with CaF
2, EuF
2for raw material, by CaF
2with EuF
2fixed molar ratio 0.995:0.005 mixed grinding, under in box-type furnace, Ar atmosphere encloses protection afterwards, 900 DEG C insulation 2 hours, furnace cooling, prepares Ca
0.995eu
0.005f
2middle powder.Then with PbF
2and Ca
0.995eu
0.005f
2for PbF pressed by raw material
2with Ca
0.995eu
0.005f
2mol ratio is 0.8:0.2 mixed grinding, adds PTFE reductor, and in box-type furnace, Ar atmosphere to enclose under protection 550 DEG C of insulations 3 hours, and furnace cooling, prepares Pb
0.8ca
0.199eu
0.001f
2(550) sample.
As shown in Fig. 5 (a), Pb
0.8ca
0.199eu
0.001f
2(550) sample is under 336nm excites, and has very strong luminous zone at 422nm place, is Eu
2+4f
65d
1→ 4f
7the characteristic luminescence band of transition; Under 392nm excites, the characteristic luminescence band that 422nm place is stronger still derives from Eu
2+4f
65d
1→ 4f
7transition, can find out there is very weak glow peak at 591nm by enlarged view (Fig. 5 (b)), come from Eu
3+'s
5d
0→
7f
1transition; Eu in sample
2+and Eu
3+the ratio of characteristic luminescence integrated intensity be 101.3:1, interpret sample Pb
0.8ca
0.199eu
0.001f
2(550) the Eu ion major part in is with Eu
2+form exist, only have the Eu of seldom amount
3+exist.
Embodiment 6
At 550 DEG C (lower than PbF
2fusing point---824 DEG C) treatment temp under prepare the Pb of serial different levels of doping
1- x(Ca
0.995eu
0.005)
xf
2(550) (x=0,1%, 5%, 10%, 15%) powder sample.
First with CaF
2, EuF
2for raw material, by CaF
2with EuF
2mol ratio be 0.995:0.005 mixed grinding, in box-type furnace, Ar atmosphere to enclose under protection 900 DEG C of insulations 2 hours, prepares Ca
0.995eu
0.005f
2middle powder; Then with PbF
2, Ca
0.995eu
0.005f
2for raw material, by PbF
2with Ca
0.995eu
0.005f
2mol ratio be (1-x): x mixed grinding, adds PTFE reductor, and in box-type furnace, Ar atmosphere to enclose under protection 550 DEG C of insulations 3 hours, prepares the sample P b of serial different levels of doping
1-x(Ca
0.995eu
0.005)
xf
2(550) (x=0,1%, 5%, 10%, 15%).
As shown in Fig. 6 (a), under the optical excitation of 336nm wavelength, work as Ca
0.995eu
0.005f
2mole doped parameterx=1% time, Pb
1-x(Ca
0.995eu
0.005)
xf
2(550) luminescence of sample near 422nm is very weak, when x>=5%, and Pb
1- x(Ca
0.995eu
0.005)
xf
2(550) sample has obvious Eu near 422nm
2+4f
65d
1→ 4f
7the characteristic luminescence band of transition, and along with the further increase of doping content, the luminous intensity of sample strengthens thereupon; As shown in Fig. 6 (b), under the optical excitation of 392nm wavelength, Pb
1-x(Ca
0.995eu
0.005)
xf
2(550) sample still come from Eu at the stronger luminous zone at 420nm place
2+4f
65d
1→ 4f
7transition, at 591nm place, very weak glow peak comes from Eu
3+'s
5d
0→
7f
1transition, Pb
1- x(Ca
0.995eu
0.005)
xf
2(550) Eu in sample
2+and Eu
3+the ratio of characteristic luminescence integrated intensity be 7.8:1 (x=5%), 14.1:1 (x=10%), 25.7:1 (x=15%), sample P b under the treatment temp of 550 DEG C
1- x(Ca
0.995eu
0.005)
xf
2(550) the Eu ion major part in (x>=5%) is with Eu
2+form exist, only have the Eu of seldom amount
3+exist.
Industrial applicability: the present invention will have the Eu of band spectrum, fast decay
2+characteristic luminescence (5d-4f transition) and high-density, relative low price Cherenkov twinkler---the PbF of excellence
2combine, can be used for PbF
2the two development reading material (crystal/glass/ceramic) of base, will have very important practical value in study of high energy physics and Application Areas.
Claims (10)
1. one kind has Eu
2+the PbF of characteristic luminescence
2sill, is characterized in that, the chemical constitution general formula of described material is Pb
1-x(Ca
1-yeu
y)
xf
2, wherein 0.005≤y≤0.05, x>=0.05, described material is with PbF
2for matrix, with Ca
1-yeu
yfor co-dopant obtains through codoped thermal treatment, described co-dopant Ca
1-yeu
ywith CaF
2for matrix, EuF
2or EuF
3for doping agent thermal treatment at 800 ~ 900 DEG C obtains.
2. according to claim 1 have Eu
2+the PbF of characteristic luminescence
2sill, is characterized in that, when the heat treated temperature of described codoped is greater than PbF
2fusing point time, x>=0.2.
3. according to claim 1 and 2 have Eu
2+the PbF of characteristic luminescence
2sill, is characterized in that, y is 0.03.
4. according to any one of claims 1 to 3, there is Eu
2+the PbF of characteristic luminescence
2sill, is characterized in that, Eu in described material
2+characteristic luminescence and Eu
3+the strength ratio of characteristic luminescence is (2 ~ 110): 1.
5. according to any one of Claims 1 to 4, there is Eu
2+the PbF of characteristic luminescence
2sill, is characterized in that, described Eu
2+characteristic luminescence is the characteristic luminescence band of the 390 ~ 500nm produced under 320 ~ 400nm optical excitation.
6. according to any one of a Claims 1 to 5, there is Eu
2+the PbF of characteristic luminescence
2the preparation method of sill, is characterized in that, comprising:
(1) with CaF
2for matrix, EuF
2or EuF
3for doping agent, by after stoicheiometry mixed grinding in 800 ~ 900 DEG C under protection of inert gas thermal treatment obtain co-dopant (Ca
1-yeu
y) F
2; And
(2) with PbF
2for matrix, with (Ca
1-yeu
y) F
2for co-dopant, after stoicheiometry mixed grinding, described in obtained through codoped thermal treatment under protection of inert gas and under the existence of reductor, there is Eu
2+the PbF of characteristic luminescence
2sill.
7. preparation method according to claim 6, is characterized in that, in described step (2), the heat treated temperature of described codoped is 500 ~ 1000 DEG C, and the time is 0.5 ~ 3 hour.
8. preparation method according to claim 7, is characterized in that, in described step (2), when the heat treated temperature of described codoped is higher than described PbF
2fusing point time, (Ca
1-yeu
y) F
2with PbF
2mol ratio be more than 1/4.
9. the preparation method according to any one of claim 6 ~ 8, is characterized in that, described reductor is tetrafluoroethylene.
10. the preparation method according to any one of claim 6 ~ 9, is characterized in that, in described step (1), the heat treated time is 1 ~ 2 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110541198A (en) * | 2018-05-29 | 2019-12-06 | 中国科学院上海硅酸盐研究所 | Europium ion doped fluoride crystal with display color gamut capable of being regulated and controlled in large range and preparation method thereof |
| CN113403065A (en) * | 2021-04-30 | 2021-09-17 | 河北大学 | Fluoride-based stress luminescent material, preparation method and application thereof |
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Cited By (3)
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| CN110541198A (en) * | 2018-05-29 | 2019-12-06 | 中国科学院上海硅酸盐研究所 | Europium ion doped fluoride crystal with display color gamut capable of being regulated and controlled in large range and preparation method thereof |
| CN113403065A (en) * | 2021-04-30 | 2021-09-17 | 河北大学 | Fluoride-based stress luminescent material, preparation method and application thereof |
| CN113403065B (en) * | 2021-04-30 | 2022-11-18 | 河北大学 | Fluoride-based stress luminescent material, preparation method and application thereof |
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