CN107142107A - It is a kind of while launching long-afterglow material of visible ray and near infrared light and preparation method thereof - Google Patents
It is a kind of while launching long-afterglow material of visible ray and near infrared light and preparation method thereof Download PDFInfo
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- CN107142107A CN107142107A CN201710590836.5A CN201710590836A CN107142107A CN 107142107 A CN107142107 A CN 107142107A CN 201710590836 A CN201710590836 A CN 201710590836A CN 107142107 A CN107142107 A CN 107142107A
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- 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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7767—Chalcogenides
- C09K11/7769—Oxides
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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
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
- C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
Abstract
Launch visible ray and the photoemissive long-afterglow material of near-infrared and preparation method simultaneously the invention provides a kind of, the material has formula：A2‑a‑b‑cO2S:aYb,bM,cT；A=0.00001~0.02, b=0.0001~0.03, c=0.0001~0.03；One or more of the A in Y, Sc, La, Gd and Lu；One or more of the M in Zn, Mg, Ca, Sr and Ba；One or more of the T in V, Nb, Ta, Ti, Zr, Hf, Cr, Mo and W.The material is using Yb as light emitting ionic, and M and T are co-dopant ions, and N is fluxing and catalytic ionic so that the luminescent material can effectively be excited by ultraviolet light, while producing the long-persistence luminous of visible ray and near infrared light, persistence is long；Physical and chemical stability is good, nontoxic, "dead", to human body and environment non-hazardous.
Description
Technical field
The present invention relates to long after glow luminous material technical field, more particularly to a kind of transmitting visible ray and near infrared light simultaneously
Long-afterglow material and preparation method thereof.
Background technology
Long after glow luminous material, be it is a kind of can store the energy of extraneous light radiation such as ultraviolet light and visible ray etc., then
It is slow at room temperature that these materials for storing energy are discharged in the form of luminous.Newest result of study shows long-afterglow material
Indicated in living body biological imaging, AC LED, dim light and display field has important application value.
Come in as application potential of the near-infrared long-afterglow material in terms of medical imaging is increasingly highlighted, near-infrared long afterglow
Material causes researcher greatly to pay close attention to.But the long-afterglow material species of near-infrared luminous (NIR, 700nm~1000nm) compared with
Few, current existing near-infrared long after glow luminous material is the ion-activated luminescent materials of Cr, for example《What a kind of Cr adulterated receives
Rice near-infrared long-afterglow material and preparation method thereof》(Chinese invention patent, 201410127225.3),《A kind of trivalent chromic ion
Zinc stannate near-infrared long after glow luminous material of doping and preparation method thereof》(Chinese invention patent, 201410127473.8) with
And the new material ZnGa reported in academic documents2O4:Cr3+(Opt.Express 2011,19,10131-10137.) and
La3Ga5GeO14:Cr3+(Opt.Express 2010,18,20215-20221.) etc..But because the Cr ions of high price are easily right
Ecological environment produces harm, therefore urgently develops new near-infrared long-afterglow material.
In the prior art, a kind of borate glass ion-activated Yb has the long-persistence luminous of near-infrared
(J.Appl.Phys.2007,101,113304.), but luminescent powder ion-activated Yb is but very rare.Especially can be simultaneously
The long-afterglow material for launching visible ray and near infrared light is even more to have no report.
The content of the invention
In view of this, it is an object of the invention to provide a kind of long-afterglow material and preparation method thereof, this is long-persistence luminous
Material can produce long-persistence luminous, persistence length, the brightness height of visible ray and near infrared light simultaneously.
The invention provides a kind of long after glow luminous material, with formula shown in Formulas I：
A2-a-b-cO2S:AYb, bM, cT Formulas I；
In Formulas I, a=0.00001~0.02, b=0.001~0.03, c=0.001~0.03；
One or more of the A in Y, Sc, La, Gd and Lu；
One or more of the M in Zn, Mg, Ca, Sr and Ba；
One or more of the T in V, Nb, Ta, Ti, Zr, Hf, Cr, Mo and W.
Preferably, a=0.00001~0.01.
Preferably, b=0.001~0.02.
Preferably, c=0.001~0.02.
The invention provides a kind of preparation method of long after glow luminous material described in above-mentioned technical proposal, including following step
Suddenly：
By A source compounds, Yb source compounds, M source compounds, T source compounds, elemental sulfur and N source compound mixed grindings
After uniform, roasting obtains long after glow luminous material.
Preferably, the A source compounds include the oxide containing A, the carbonate containing A, the oxalates containing A, the chlorination containing A
One or more in thing, the sulfate containing A, the nitrate containing A and the acetate containing A；
The M sources include the oxide containing M, the carbonate containing M, the oxalates containing M, the chloride containing M, the sulfuric acid containing M
One or more in salt, the nitrate containing M and the acetate containing M.
Preferably, the T sources include the one or more in the oxide containing T, the ammonium salt containing T and the hydrochlorate containing T；
The N sources include the oxide containing N, the chloride containing N, the carbonate containing N, the oxalates containing N, the phosphoric acid containing N
One or more in salt, the sulfate containing N, the nitrate containing N and the acetate containing N.
Preferably, the temperature of the roasting is 900~1400 DEG C；The time of the roasting is 0.5~24h.
Preferably, also include after the roasting：
By obtained product of roasting after water and watery hydrochloric acid washing, long after glow luminous material is obtained.
Preferably, the roasting is carried out under particular atmosphere；The particular atmosphere is carbon monoxide, hydrogen, the mixing of nitrogen hydrogen
Gas or H2S gases.
The invention provides a kind of long after glow luminous material, with formula shown in Formulas I：A2-a-b-cO2S:AYb, bM, cT Formulas I；
In Formulas I, a=0.00001~0.02, b=0.001~0.03, c=b=0.001~0.03；The A be selected from Y, Sc, La,
One or more in Gd and Lu；One or more of the M in Zn, Mg, Ca, Sr and Ba；The T be selected from V, Nb, Ta,
One or more in Ti, Zr, Hf, Cr, Mo and W.The long after glow luminous material that the present invention is provided using oxysulfide as matrix, with
Yb ions are light emitting ionic, and using M and T as co-dopant ions, using N as fluxing and catalytic ionic, synthesized luminescent material can
Effectively excited by ultraviolet light, while producing long-persistence luminous, persistence length, the brightness height of visible ray and near infrared light.This hair
The long after glow luminous material physical and chemical stability of bright offer is good, nontoxic, "dead", and human body and environment will not be produced
Harm.Test result indicates that：Long after glow luminous material by after ultraviolet excitation, the transmitting of its twilight sunset have simultaneously VISIBLE LIGHT EMISSION and
Near infrared light is launched, and persistence is more than 5h.
Brief description of the drawings
Fig. 1 is to have visible ray and near-infrared luminous long after glow luminous material while obtain in the embodiment of the present invention 1
In the excitation and emission spectra figure of visible ray section；
Fig. 2 has visible ray while being obtained for the embodiment of the present invention 1 and near-infrared luminous long after glow luminous material exists
The launching light spectrogram and its exciting light spectrogram of near infrared band；
Fig. 3 has visible ray while being obtained for the embodiment of the present invention 1 and near-infrared luminous long-afterglow material is ultraviolet
Light excite after visible near infrared band long-after-glow light spectrogram；
Fig. 4 is to have visible ray and near-infrared luminous long after glow luminous material while obtain in the embodiment of the present invention 2
In the excitation and emission spectra figure of visible ray section.
Embodiment
The invention provides a kind of long after glow luminous material, with formula shown in Formulas I：
A2-a-b-cO2S:AYb, bM, cT Formulas I；
In Formulas I, a=0.00001~0.02, b=0.001~0.03, c=0.001~0.03；
One or more of the A in Y, Sc, La, Gd and Lu；
One or more of the M in Zn, Mg, Ca, Sr and Ba；
One or more of the T in V, Nb, Ta, Ti, Zr, Hf, Cr, Mo and W.
The long after glow luminous material that the present invention is provided is using oxysulfide as matrix, using Yb ions as light emitting ionic, with M and T
For co-dopant ions, using N as fluxing and catalytic ionic, synthesized luminescent material can effectively be excited by ultraviolet light, be produced simultaneously
Long-persistence luminous, persistence length, the brightness height of raw visible ray and near infrared light.The long after glow luminous material thing that the present invention is provided
Physicochemical stability is good, nontoxic, "dead", will not be to human body and environmental danger.
In the present invention, a, b, c are molar percentage of the corresponding Doped ions with respect to A ions；Described 0.00001~
0.02, it is preferable that a=0.00001~0.01, it is highly preferred that a=0.0001~0.001.There is provided in the present invention
In some embodiments, a is preferably a=0.0001；In some embodiments that the present invention is provided, a is preferably a=
0.0005。
In the present invention, b=0.001~0.03, it is preferable that b=0.001~0.02, it is highly preferred that described
B=0.001~0.01；In some embodiments that the present invention is provided, the b is preferably b=0.01.
In the present invention, c=0.001~0.03, it is preferable that c=0.001~0.02, it is highly preferred that described
C=0.001~0.01.In some embodiments that the present invention is provided, the c is preferably c=0.01.
In the present invention, one or more of the A in Y, Sc, La, Gd and Lu；The A be preferably selected from Y, Sc and
One or more in Lu；In a particular embodiment of the present invention, the A is specially Y.Some embodiments provided in the present invention
In, the A is specially Lu；In some embodiments that the present invention is provided, the A is specially Sc；Some provided in the present invention
In embodiment, the A is preferably Y and Lu；In some embodiments that the present invention is provided, the A is specially Y and Sc.
In the present invention, one or more of the M in Zn, Mg, Ca, Sr and Ba；Preferably, the M is selected from Mg
Or/and Ca.In some embodiments that the present invention is provided, the M is specially Ca；In some embodiments that the present invention is provided,
The M is specially Mg；In some embodiments that the present invention is provided, the M is specially Ca and Mg.
In the present invention, one or more of the T in V, Nb, Ta, Ti, Zr, Hf, Cr, Mo and W；Preferably, institute
State T and be selected from Ti or/and V.In some embodiments that the present invention is provided, the T is specially Ti；Some realities provided in the present invention
Apply in example, the T is specially V；In some embodiments that the present invention is provided, the T is specially Ti and V.
In some embodiments that the present invention is provided, the long after glow luminous material is specially Y2-0.0001-0.01-0.01O2S:
0.0001Yb, 0.01Ca, 0.01Ti；In some embodiments that the present invention is provided, the long after glow luminous material is specially
Lu2-0.0005-0.01-0.01O2S:0.0005Yb, 0.01Mg, 0.01Ti；In some embodiments that the present invention is provided, more than the length
Brightness luminescent material is specially Sc2-0.0001-0.01-0.01O2S:0.0001Yb, 0.01Ca, 0.01Ti；Some realities provided in the present invention
Apply in example, the long after glow luminous material is specially (Y, Lu)2-0.0001-0.01-0.01O2S:0.0001Yb, 0.01Mg, 0.01Ti；
In some embodiments that the present invention is provided, the long after glow luminous material is specially (Y, Sc)2-0.0001-0.01-0.01O2S:
0.0001Yb, 0.01Ca, 0.01Ti；In some embodiments that the present invention is provided, the long after glow luminous material is specially
Y2-0.0001-0.01-0.01O2S:0.0001Yb, 0.01Mg, 0.01V；In some embodiments that the present invention is provided, the long afterglow
Luminescent material is specially Lu2-0.0001-0.01-0.01O2S:0.0001Yb, 0.01Ca, 0.01V；Some implementations provided in the present invention
In example, the long after glow luminous material is specially Sc2-0.0001-0.01-0.01O2S:0.0001Yb, 0.01Ca, 0.01 (Ti, V).
The long after glow luminous material that the present invention is provided is using oxysulfide as matrix, and Yb passes through codope M as light emitting ionic
Visible ray and near-infrared long afterglow qualities are obtained with T ions, the luminescent material has persistence length, brightness high, physico
Learn stability it is good, nontoxic, it is "dead" the advantages of, and do not contain the metal ion for having harm to human body and environment.
The invention provides a kind of preparation method of long after glow luminous material described in above-mentioned technical proposal, including following step
Suddenly：
By A source compounds, Yb source compounds, M source compounds, T source compounds, elemental sulfur and N source compound mixed grindings
After uniform, roasting obtains long after glow luminous material.
In the present invention, the A source compounds preferably include the oxide containing A, the carbonate containing A, the oxalates containing A,
One or more in chloride containing A, the sulfate containing A, the nitrate containing A and the acetate containing A；More preferably containing A's
Oxide and/or the carbonate containing A, are most preferably the oxide containing A.
In the present invention, the Yb is near-infrared light emitting ionic.The Yb source compounds preferably include the oxide containing Yb,
One or more in carbonate containing Yb, the nitrate containing Yb, the phosphate containing Yb and the chloride containing Yb；More preferably contain
One or more in Yb oxide, the carbonate containing Yb and the phosphate containing Yb；Oxide most preferably containing Yb and/or
Carbonate containing Yb.
In the present invention, the M sources preferably include the oxide containing M, the carbonate containing M, the oxalates containing M, the chlorine containing M
One or more in compound, the sulfate containing M, the nitrate containing M and the acetate containing M；More preferably include the oxidation containing M
One or more in thing, the carbonate containing M and the oxalates containing M；Oxide most preferably containing M and/or the carbonic acid containing M
Salt.
In the present invention, the T sources preferably include the oxide containing T, the ammonium salt containing T and one kind in the hydrochlorate containing T or
It is a variety of；More preferably include the oxide containing T and/or the hydrochlorate containing T.
In the present invention, the N sources preferably include the oxide containing N, the chloride containing N, the carbonate containing N, the grass containing N
One or more in hydrochlorate, the phosphate containing N, the sulfate containing N, the nitrate containing N and the acetate containing N；More preferably wrap
Include the one or more in the oxide containing N, the carbonate containing N and the oxalates containing N；Most preferably include oxide containing N and/
Or the carbonate containing N.
In the present invention, the addition of the elemental sulfur is A source compounds, Yb source compounds, M source compounds, T sources chemical combination
The 50%~500% of gross mass after thing mixing；The addition in the N sources is A source compounds, Yb source compounds, M source compounds, T
The 10%~200% of gross mass after source compound mixing.
In the present invention, the roasting is carried out under particular atmosphere；The particular atmosphere is carbon monoxide, hydrogen, nitrogen hydrogen
Gaseous mixture or H2S gases.
In the present invention, the temperature of the roasting is preferably 800~1400 DEG C, more preferably 1000~1300 DEG C；It is described
The time of roasting is preferably 0.5~24h, more preferably 2~6h, most preferably 4h.
In the present invention, preferably also include after the roasting：
By obtained product of roasting after water and watery hydrochloric acid washing, long after glow luminous material is obtained.
The present invention preferably first cools down obtained product of roasting, is washed again by water and watery hydrochloric acid after grinding.The present invention is excellent
Choosing is ground using disintegrating machine well known to those skilled in the art and grinder.
In the present invention, the crude product obtained after cooling and grinding is entered into water-filling and the washing of watery hydrochloric acid, its specific mistake
Journey includes：
Crude product is placed in container, distilled water or deionized water or running water immersion is added, stirs 1~10 minute, it is excellent
Elect as 5 minutes, stand or centrifugation removes supernatant, repeat 1~3 time；Preferably 2 times；
Then 1~3 time, the preferably watery hydrochloric acid of volume ratio 2% are washed with the diluted hydrochloric acid aqueous solution of volume ratio 1%~5%
Washing 2 times；
Finally it is washed with water and washs 1~3 time, then dries or dry naturally, obtain long after glow luminous material.
The long after glow luminous material that the present invention is provided is using oxysulfide as matrix, using Yb ions as light emitting ionic, with M and T
For co-dopant ions, using N as fluxing and catalytic ionic, synthesized luminescent material can effectively be excited by ultraviolet light, be produced simultaneously
Long-persistence luminous, persistence length, the brightness height of raw visible ray and near infrared light.The long after glow luminous material thing that the present invention is provided
Physicochemical stability is good, nontoxic, "dead", will not be to human body and environmental danger.Test result indicates that：Long afterglow
Luminescent material is by after ultraviolet excitation, and the transmitting of its twilight sunset has VISIBLE LIGHT EMISSION and near infrared light transmitting simultaneously, and persistence is
More than 5h.
In order to further illustrate the present invention, with reference to a kind of provide the present invention of embodiment and meanwhile launch visible ray and
Long-afterglow material of near infrared light and preparation method thereof is described in detail, but can not be interpreted as them to present invention protection
The restriction of scope.
Embodiment 1
Take Y2O3(analysis is pure), Yb2O3(analysis is pure), CaCO3(analysis is pure), TiO2(analysis is pure) is according to mol ratio (2-
0.0001-0.01-0.01):0.0001:0.02:0.02 weighs mixing, adds the Na of said mixture quality 30%2CO3(point
Analysis it is pure) and the elemental sulfur of said mixture quality 100% be fully ground uniformly, obtain initial feed mixture.
The initial feed mixture is placed in corundum crucible, the above-mentioned corundum crucible equipped with mixture is put into height
In warm stove, in presence of hydrogen, roasting 4h is carried out in 1200 DEG C, naturally cool to room temperature, taken out crushing grinding uniformly, obtain powder
Last shape long afterglow crude product；Crude product is long after glow luminous material Y after water and watery hydrochloric acid washing2-0.0001-0.01- 0.01O2S:0.0001Yb, 0.01Ca, 0.01Ti.
Excitation spectrum, emission spectrum and twilight sunset spectrum test, knot are carried out to the long after glow luminous material obtained in embodiment 1
Fruit is referring to Fig. 1~3.Wherein, Fig. 1 be there is visible ray while obtain in the embodiment of the present invention 1 and near-infrared luminous length more than
Excitation and emission spectra figure of the brightness luminescent material in visible ray section；Fig. 2 is that the embodiment of the present invention 1 has visible ray while obtaining
With near-infrared luminous long after glow luminous material near infrared band launching light spectrogram and its exciting light spectrogram；Fig. 3 is this hair
Bright embodiment 1 there is visible ray while obtaining and near-infrared luminous long after glow luminous material after ultraviolet excitation visible
To the long-after-glow light spectrogram of near infrared band.Instrument is the FLS-980 XRFs that Edinburgh, Britain company produces.By
Fig. 1 understands that the long after glow luminous material can effectively be excited by ultraviolet light, and its emission spectra is positioned at 450nm and is located at
650nm or so VISIBLE LIGHT EMISSION, charge migration transition transmitting of the transmitting from Yb ions.As shown in Figure 2, the long afterglow
Luminescent material can effectively be excited by ultraviolet light, and its emission spectra be positioned at 980nm near infrared emission, the transmitting from Yb from
The f-f transition transmitting of son.Twilight sunset spectrum of the long after glow luminous material after 254nm ultraviolet excitations is tested, instrument is U.S.
The NIRqust fiber spectrometers of state's marine optics production.From the figure 3, it may be seen that the near-infrared luminous of long after glow luminous material belongs to
Yb3+Ion2F7/2→2F5/2Transition, it is seen that charge migration transmitting of the light transmitting from Yb ions.Test result shows, implements
The persistence of the long after glow luminous material obtained in example 1 is more than 5h.
Embodiment 2
Take Lu2O3(analysis is pure), Yb2O3(analysis is pure), MgCO3(analysis is pure), TiO2(analysis is pure) is according to mol ratio (2-
0.0005-0.01-0.01):0.0005:0.02:0.02 weighs mixing, adds the Na of said mixture quality 30%2CO3(point
Analysis it is pure) and the elemental sulfur of said mixture quality 100% be fully ground uniformly, obtain initial feed mixture；
The initial feed mixture is placed in corundum crucible, the above-mentioned corundum crucible equipped with mixture is put into height
In warm stove, in presence of hydrogen, roasting 4h is carried out in 1200 DEG C, naturally cool to room temperature, taken out crushing grinding uniformly, obtain powder
Last shape long afterglow crude product；Crude product is long after glow luminous material Lu after water and watery hydrochloric acid washing2-0.0005-0.01- 0.01O2S:0.0005Yb, 0.01Mg, 0.01Ti.
Excitation spectrum, emission spectrum and twilight sunset spectrum test are carried out to the long after glow luminous material obtained in embodiment 2, is seen
Fig. 4, Fig. 4 for the present invention in obtain while there is visible ray and near-infrared luminous long after glow luminous material visible ray section
Excitation and emission spectra figure.Test result shows that long after glow luminous material can effectively be excited by ultraviolet light, and its emission spectra is
The broadband emission of the transmitting of near-infrared wire and visible region near 980nm.
The long after glow luminous material obtained after tested in embodiment 2 is by after ultraviolet excitation, and the transmitting of its twilight sunset has simultaneously
VISIBLE LIGHT EMISSION and near infrared light transmitting, the persistence of sample is more than 5h.
Embodiment 3
Take Sc2O3(analysis is pure), Yb2O3(analysis is pure), CaCO3(analysis is pure), TiO2(analysis is pure) is according to mol ratio (2-
0.0001-0.01-0.01):0.0001:0.02:0.02 weighs mixing, adds the Li of said mixture quality 30%2CO3(point
Analysis it is pure) and the elemental sulfur of said mixture quality 100% be fully ground uniformly, obtain initial feed mixture.
The initial feed mixture is placed in corundum crucible, the above-mentioned corundum crucible equipped with mixture is put into height
In warm stove, in presence of hydrogen, roasting 4h is carried out in 1200 DEG C, naturally cool to room temperature, taken out crushing grinding uniformly, obtain powder
Last shape long afterglow crude product；Crude product is long after glow luminous material Sc after water and watery hydrochloric acid washing2-0.0001-0.01- 0.01O2S:0.0001Yb, 0.01Ca, 0.01Ti.
The long after glow luminous material obtained after tested in embodiment 3 is by after ultraviolet excitation, and the transmitting of its twilight sunset has simultaneously
VISIBLE LIGHT EMISSION and near infrared light transmitting, the persistence of sample is more than 5h.
Embodiment 4
Take Y2O3(analysis is pure), Lu2O3(analysis is pure), Yb2O3(analysis is pure), MgCO3(analysis is pure), TiO2(analysis is pure) presses
According to mol ratio 1:(1-0.0001-0.01-0.01):0.0001:0.02:0.02 weighs mixing, adds said mixture quality
30% K2CO3(analysis is pure) and the elemental sulfur of said mixture quality 100% are fully ground uniformly, obtain initial feed mixing
Thing.
The initial feed mixture is placed in corundum crucible, the above-mentioned corundum crucible equipped with mixture is put into height
In warm stove, in presence of hydrogen, roasting 4h is carried out in 1200 DEG C, naturally cool to room temperature, taken out crushing grinding uniformly, obtain powder
Last shape long afterglow crude product；Crude product by water and watery hydrochloric acid washing after be long after glow luminous material (Y,
Lu)2-0.0001-0.01-0.01O2S:0.0001Yb, 0.01Mg, 0.01Ti.
The long after glow luminous material obtained after tested in embodiment 4 is by after ultraviolet excitation, and the transmitting of its twilight sunset has simultaneously
VISIBLE LIGHT EMISSION and near infrared light transmitting, the persistence of sample is more than 5h.
Embodiment 5
Take Y2O3(analysis is pure), Sc2O3(analysis is pure), Yb2O3(analysis is pure), CaCO3(analysis is pure), TiO2(analysis is pure) presses
According to mol ratio 1:(1-0.0001-0.01-0.01):0.0001:0.02:0.02 weighs mixing, adds said mixture quality
30% Na2CO3(analysis is pure) and the elemental sulfur of said mixture quality 100% are fully ground uniformly, obtain initial feed mixing
Thing.
The initial feed mixture is placed in corundum crucible, the above-mentioned corundum crucible equipped with mixture is put into height
In warm stove, in presence of hydrogen, roasting 4h is carried out in 1200 DEG C, naturally cool to room temperature, taken out crushing grinding uniformly, obtain powder
Last shape long afterglow crude product；Crude product by water and watery hydrochloric acid washing after be long after glow luminous material (Y,
Sc)2-0.0001-0.01-0.01O2S:0.0001Yb, 0.01Ca, 0.01Ti.
The long after glow luminous material obtained after tested in embodiment 5 is by after ultraviolet excitation, and the transmitting of its twilight sunset has simultaneously
VISIBLE LIGHT EMISSION and near infrared light transmitting, the persistence of sample is more than 5h.
Embodiment 6
Take Y2O3(analysis is pure), Yb2O3(analysis is pure), MgCO3(analysis is pure), V2O5(analysis is pure) is according to mol ratio (2-
0.0001-0.01-0.01):0.0001:0.02:0.01 weighs mixing, adds the Na of said mixture quality 30%2CO3(point
Analysis it is pure) and the elemental sulfur of said mixture quality 100% be fully ground uniformly, obtain initial feed mixture.
The initial feed mixture is placed in corundum crucible, the above-mentioned corundum crucible equipped with mixture is put into height
In warm stove, in presence of hydrogen, roasting 4h is carried out in 1200 DEG C, naturally cool to room temperature, taken out crushing grinding uniformly, obtain powder
Last shape long afterglow crude product；Crude product is long after glow luminous material Y after water and watery hydrochloric acid washing2-0.0001-0.01- 0.01O2S:0.0001Yb, 0.01Mg, 0.01V.
The long after glow luminous material obtained after tested in embodiment 6 is by after ultraviolet excitation, and the transmitting of its twilight sunset has simultaneously
VISIBLE LIGHT EMISSION and near infrared light transmitting, the persistence of sample is more than 5h.
Embodiment 7
Take Lu2O3(analysis is pure), Yb2O3(analysis is pure), CaCO3(analysis is pure), V2O5(analysis is pure) is according to mol ratio (2-
0.0001-0.01-0.01):0.0001:0.02:0.01 weighs mixing, adds the Na of said mixture quality 30%2CO3(point
Analysis it is pure) and the elemental sulfur of said mixture quality 100% be fully ground uniformly, obtain initial feed mixture.
The initial feed mixture is placed in corundum crucible, the above-mentioned corundum crucible equipped with mixture is put into height
In warm stove, in presence of hydrogen, roasting 4h is carried out in 1200 DEG C, naturally cool to room temperature, taken out crushing grinding uniformly, obtain powder
Last shape long afterglow crude product；Crude product is long after glow luminous material Lu after water and watery hydrochloric acid washing2-0.0001-0.01- 0.01O2S:0.0001Yb, 0.01Ca, 0.01V.
The long after glow luminous material obtained after tested in embodiment 7 is by after ultraviolet excitation, and the transmitting of its twilight sunset has simultaneously
VISIBLE LIGHT EMISSION and near infrared light transmitting, the persistence of sample is more than 5h.
Embodiment 8
Take Sc2O3(analysis is pure), Yb2O3(analysis is pure), CaCO3(analysis is pure), TiO2(analysis is pure), V2O5(analysis is pure) presses
According to mol ratio (2-0.0001-0.01-0.01):0.0001:0.02:0.01:0.005 weighs mixing, adds said mixture
The Na of quality 30%2CO3(analysis is pure) and the elemental sulfur of said mixture quality 100% are fully ground uniformly, obtain initial feed
Mixture.
The initial feed mixture is placed in corundum crucible, the above-mentioned corundum crucible equipped with mixture is put into height
In warm stove, in presence of hydrogen, roasting 4h is carried out in 1200 DEG C, naturally cool to room temperature, taken out crushing grinding uniformly, obtain powder
Last shape long afterglow crude product；Crude product is long after glow luminous material Sc after water and watery hydrochloric acid washing2-0.0001-0.01- 0.01O2S:0.0001Yb, 0.01Ca, 0.01 (Ti, V).
The long after glow luminous material obtained after tested in embodiment 8 is by after ultraviolet excitation, and the transmitting of its twilight sunset has simultaneously
VISIBLE LIGHT EMISSION and near infrared light transmitting, the persistence of sample is more than 5h.
As seen from the above embodiment, the invention provides a kind of long after glow luminous material, with formula shown in Formulas I：
A2-a-b-cO2S:AYb, bM, cT Formulas I；In Formulas I, a=0.00001~1, b=0.0001~0.2, c=0.0001~0.2；
One or more of the A in Y, Sc, La, Gd and Lu；One or more of the M in Zn, Mg, Ca, Sr and Ba；
One or more of the T in V, Nb, Ta, Ti, Zr, Hf, Cr, Mo and W.The long after glow luminous material that the present invention is provided with
Oxysulfide is matrix, using Yb ions as light emitting ionic, using M and T as co-dopant ions, using N as fluxing and catalytic ionic, is closed
Into luminescent material can effectively be excited by ultraviolet light, while the long-persistence luminous of visible ray and near infrared light is produced, during twilight sunset
Between long, brightness it is high.The long after glow luminous material physical and chemical stability that the present invention is provided is good, nontoxic, "dead", will not
To human body and environmental danger.Test result indicates that：Long after glow luminous material is by after ultraviolet excitation, and its twilight sunset is launched simultaneously
Launch with VISIBLE LIGHT EMISSION and near infrared light, persistence is more than 5h.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of long after glow luminous material, with formula shown in Formulas I：
A2-a-b-cO2S:AYb, bM, cT Formulas I；
In Formulas I, a=0.00001~0.02, b=0.0001~0.03, c=0.0001~0.03；
One or more of the A in Y, Sc, La, Gd and Lu；
One or more of the M in Zn, Mg, Ca, Sr and Ba；
One or more of the T in V, Nb, Ta, Ti, Zr, Hf, Cr, Mo and W.
2. long after glow luminous material according to claim 1, it is characterised in that a=0.00001~0.01.
3. long after glow luminous material according to claim 1, it is characterised in that b=0.001~0.02.
4. long after glow luminous material according to claim 1, it is characterised in that c=0.001~0.02.
5. the preparation method of long after glow luminous material, comprises the following steps described in a kind of claim 1：
A source compounds, Yb source compounds, M source compounds, T source compounds, elemental sulfur and N source compound mixed grindings is uniform
Afterwards, it is calcined, obtains long after glow luminous material.
6. preparation method according to claim 5, it is characterised in that the A source compounds include the oxide containing A, containing A
Carbonate, the oxalates containing A, the chloride containing A, the sulfate containing A, the nitrate containing A and the acetate containing A in one kind
Or it is a variety of；
The M sources include the oxide containing M, the carbonate containing M, the oxalates containing M, the chloride containing M, the sulfate containing M, contained
One or more in M nitrate and the acetate containing M.
7. preparation method according to claim 5, it is characterised in that the T sources include the oxide containing T, the ammonium salt containing T
With the one or more in the hydrochlorate containing T；
The N sources include the oxide containing N, the chloride containing N, the carbonate containing N, the oxalates containing N, the phosphate containing N, contained
One or more in N sulfate, the nitrate containing N and the acetate containing N.
8. preparation method according to claim 5, it is characterised in that the temperature of the roasting is 900~1400 DEG C；It is described
The time of roasting is 0.5~24h.
9. preparation method according to claim 5, it is characterised in that also include after the roasting：
By obtained product of roasting after water and watery hydrochloric acid washing, long after glow luminous material is obtained.
10. preparation method according to claim 5, it is characterised in that the roasting is carried out under particular atmosphere；The spy
Atmosphere is determined for carbon monoxide, hydrogen, nitrogen and hydrogen mixture or H2S gases.
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| CN113088286A (en) * | 2021-03-23 | 2021-07-09 | 北京科技大学 | Ytterbium-containing near-infrared ultra-long afterglow gallate luminescent material and preparation method thereof |
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| US10808171B2 (en) | 2018-01-30 | 2020-10-20 | Lextar Electronics Corporation | Infrared emitting fluoride phosphor and infrared light emitting device |
| WO2019153742A1 (en) * | 2018-02-12 | 2019-08-15 | 有研稀土新材料股份有限公司 | Near-infrared luminescent material and light-emitting device prepared using near-infrared luminescent material |
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| RU2730491C1 (en) * | 2019-06-27 | 2020-08-24 | Акционерное общество Научно-производственное предприятие "Интеграл" | Inorganic luminescent compound, marking using inorganic luminescent compound and information medium using inorganic luminescent compound |
| US10875006B1 (en) | 2020-08-21 | 2020-12-29 | King Abdulaziz University | Luminescent nanocomposite for ultrasensitive detection of mercury |
| CN113088286A (en) * | 2021-03-23 | 2021-07-09 | 北京科技大学 | Ytterbium-containing near-infrared ultra-long afterglow gallate luminescent material and preparation method thereof |
| CN113088286B (en) * | 2021-03-23 | 2023-03-21 | 北京科技大学 | Ytterbium-containing near-infrared ultra-long afterglow gallate luminescent material and preparation method thereof |
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