CN1202513A - Long persistence luminous sulfide material and producing method - Google Patents
Long persistence luminous sulfide material and producing method Download PDFInfo
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- CN1202513A CN1202513A CN 97111381 CN97111381A CN1202513A CN 1202513 A CN1202513 A CN 1202513A CN 97111381 CN97111381 CN 97111381 CN 97111381 A CN97111381 A CN 97111381A CN 1202513 A CN1202513 A CN 1202513A
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- 239000000463 material Substances 0.000 title claims abstract description 104
- 230000002688 persistence Effects 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims description 12
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 10
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 229910052788 barium Inorganic materials 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- 229910052691 Erbium Inorganic materials 0.000 claims description 8
- 238000001308 synthesis method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 6
- -1 oxide Chemical compound 0.000 abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 46
- 239000005132 Calcium sulfide based phosphorescent agent Substances 0.000 description 37
- 239000011572 manganese Substances 0.000 description 27
- 238000001228 spectrum Methods 0.000 description 22
- 229910052693 Europium Inorganic materials 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 238000000695 excitation spectrum Methods 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920002994 synthetic fiber Polymers 0.000 description 5
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- 229910003251 Na K Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
The luminous material has the chemical expression of MS : Eux.AyBz, where M is one of Ca, Sr, Mg and Ba or their mixture, A is one of Na, K and Ag or their mixture, x, y and z as molar concentration are 0.00001-0.005, 0.0002-2.0 and 0.0002-0.02 separately. It is prepared through mixing the carbonate, sulfate, oxide, fluoride, chloride, acetate, nitrate and hydroxide, preferably carbonate, sulfate, oxide, fluoride, and chloride of elements in the epxression and sintering in the reducing matter and atmosphere at 900-1400 deg.c for 1-5 hr. After illuminated by light, it can give out long persistence red, orange or yellow light.
Description
What the present invention relates to is long after glow luminous material, particularly long-afterglow photoluminescent and the method for making of being made up of metallic sulfide and multiple element ion thereof.
Some sulfide are that green, blue, the orange long afterglow luminescent material of matrix becomes commercialized, as ZnS:Cu (green), (CaSr) S:Bl (blue look) and (ZnCd) S:Cu (orange).Sulfide is mixed the existing many research of red illuminating material of europium, and the time of its photic steady persistence is too short, and is not with practical value, but that sulfide mixes different kinds of ions steady persistence Research on effect is few.EP0339895A1 has proposed MS:Eu, Tm (M is Ca, Sr and composition thereof) redness or orange long afterglow luminescent material, however its after removing illumination, its luminosity is low, and lacks very much (several minutes) time of persistence, thereby influences its use range.
At the defective that prior art exists, the invention provides a series of new sulfide compounds is matrix, mixes the long-afterglow photoluminescent of multiple element ion, makes its twilight sunset brighter, and the time is longer.
Can find out calcium (Ca) or/and the sulfide of strontium (Sr) is matrix from EP 033895A1, have only europium (Eu) and thulium (Tm) luminescent material under existing simultaneously after illumination, just can send long period redness or orange twilight sunset.The present invention has adopted the sulfide metal ion of matrix to comprise second family element and composition thereof on the periodic table of elements; Activator has also been selected rare earth element ion and other element ions and composition thereof for use except that europium and thulium; Also selected for use other metallic element ions to mix in addition as the 3rd component; Adopt special synthesis technique to make this luminescent material simultaneously, long after glow luminous material chemical constitution expression of the present invention is:
MS：Eux、Ay、Bz
Wherein M is selected from Ca, Sr, one or more mixtures of Mg, Ba, and A is selected from Er (erbium), Dy (dysprosium), La (lanthanum), Tm (thulium), Y (yttrium), one or more mixtures of Mn (manganese); B is selected from Na, K, one or more mixtures of Ag; X, y, z are volumetric molar concentrations; X is 0.00001-0.005; Y is 0.0002-0.02; Z is 0.0002-0.02
In product was made, the main raw material of formation matrix had adopted carbonate to add the synthesis method of carbon when being carbonate; The main raw material of formation matrix has adopted vitriol to feed H when being vitriol
2(or H
2+ N
2) or NH
3Or use the carbon method synthetic, in order to improve the quality of synthetic materials, add suitable fusing assistant, during synthetic materials as NH
4Cl, CaF
2And SrF
2Synthetic method is respectively:
1. carbonate adds the synthesis method of carbon
The element mole proportioning of its raw material that uses
M：1-1.5
S：1-5
Eu：0.00001-0.005
A：0.0002-0.02
B:0.0002-0.02NH
4Cl:0.01-0.2CaF
2Or/and SrF
2: 0.01-0.2
C：1-5
2. vitriol feeds H
2Or NH
3Or use carbon synthesis method
The element mole proportioning of its raw material that uses
M：1-1.5
S：0-5
Eu：0.00001-0.005
A：0.0002-0.02
B:0.0002-0.02NH
4Cl:0.01-0.2CaF
2Or/and SrF
2: 0.01-0.2H
2Or (2/3NH
3): 3-12 or C:1.5-6
The synthetic employing high-temperature solid phase reaction method preparation of this material, the raw materials such as carbonate, vitriol, acetate, nitrate, fluorochemical, oxyhydroxide, oxide compound, sulfide, muriate that generally will contain element in the above-mentioned expression mix, and preferably carbonate, vitriol, oxide compound, fluorochemical, muriate mix.Blending means is that raw material mechanical mill mixes, aqueous solution, and solvent (as alcohol, acetone etc.) preferably adopts mechanical mill mixing in ceramic pot and ball or agate mortar.Mixing raw material is under an amount of reducing substance and atmosphere (preferably under carbon, hydrogen, the ammonia), and under 900-1400 ℃ of temperature, sintering 0.5-50 hour, preferred 1-5 hour, burned material was through porphyrize, and sieving gets product.
The luminous afterglow measurement of this material is the diameter 50mm that earlier sample packed into, in the disk of dark 5mm, in the darkroom, keep after 5 hours, shone 20 minutes through 1000lx with the D65 standard light source, survey the relative intensity of its twilight sunset with the briliancy determinator, and press its relative intensity and its time drafting log-log graph.
In the prior art, calcium or/and the sulfide of strontium can obtain under the activation of europium can rubescent look or orange twilight sunset material, but twilight sunset very a little less than; Add thulium ion therein improving the brightness and the time expand of twilight sunset, but be limited improvement.The present invention has searched out the A component and the B component that can increase luminous after-glow brightness and time of persistence.Make the brightness of twilight sunset of this luminescent material and perdurability progress of making a breakthrough property all.In order to prove A component element ion and the effect of B component element ionic, when making luminescent material of the present invention, also prepare no A.B component element ion, no B component element ionic material, carry out the contrast of twilight sunset effect after the illumination, what test-results showed that luminescent material twilight sunset effect of the present invention compares will improve several times to tens times, its luminous time of persistence significant prolongation.
By to the emmission spectrum of MS:Eux Ay Bz system material and the measurement and the analysis of excitation spectrum, change the composition of M, after being Ca, Mg, Sr, Ba, its luminous twilight sunset color presents the variation of red-orange-Huang, the luminescent spectrum peak value changes at 720nm-560nm, and excitation spectrum is a 400nm-620nm wide band absorption spectrum, and this illustrates that this material all has absorption to visible light, material is carried out structural analysis, be the MS system.
When M=Ca is CaS:EuxAy Bz, this material mainly takes on a red color luminous, different along with the adding composition of A component (Er DyLa Tm Y Mn) and B component (Na K Ag) and concentration (x y z), its emission wavelength presents from the variation between the 620-720nm, and glow color is from light red, pale red, dark red variation.
This material significantly strengthens than preparation CaS:Eu and its luminous afterglow intensity of CaS:Eu A material under identical conditions, time is elongated, by luminous relative afterglow measurement, can obviously find out its intensity and time of persistence relational expression CaS:Eu A B＞CaS:Eu A＞CaS:Eu, experiment shows 0.00005＜y＜0.05,0.00005 all there is influence in various degree＜z＜0.05, preferred 0.0002＜y＜0.02,0.0002＜z＜0.02,0.001＜y＜0.005 wherein, 0.001＜z＜0.01 is best, when 0.0001＜x＜0.001,0.001＜y＜0.005,0.001＜z＜0.01 o'clock, its luminous afterglow intensity is more than 300% of CaS:Eu material, and time of persistence is at (the minimum visual 0.32mcd/m of intelligent's eye more than 60 minutes
2).Especially Er, Tm, Mn in the A component, the K Ag effect in the B component is remarkable, as:
CaS：Eu?Tm?K????CaS：Eu?Tm?Ag
CaS：Eu?Er?K????CaS：Eu?Er?Ag
CaS：Eu?Mn?K????CaS：Eu?Mn?Ag
There are two kinds of elements to add simultaneously in addition in A, the B component significant effect is also arranged, as:
CaS：Eu?Tm?Mn?K????CaS：Eu?Tm?Mn?Ag
CaS：Eu?Tm?Er?K????CaS：Eu?Tm?Er?Ag
CaS：Eu?Tm?Mn?K?Ag
Two kinds of addings that element is above among A, the B simultaneously also produce effect.
To be that this material of SrS:Eux Ay Bz mainly is yellowish-orange luminous as M=Sr, different along with the adding composition of A (Er Dy LaTm Y Mn) and B (Na K Ag) and concentration (x, y, z), its emission wavelength changes at 560-630nm, and glow color is from Huang, yellow orange, orange variation.
This material significantly strengthens than preparation SrS:Eu and its luminous afterglow intensity of SrS:Eu A material under identical conditions, time is elongated, by luminous relative afterglow measurement, can obviously find out its intensity and time of persistence relational expression SrS:Eu AB＞SrS:Eu A＞SrS:Eu, experiment shows 0.00005＜y＜0.05,0.00005 all there is influence in various degree＜z＜0.05, preferred 0.0002＜y＜0.02,0.0002＜z＜0.02,0.001＜y＜0.005 wherein, 0.001＜z＜0.01 is best, when 0.0001＜x＜0.001,0.001＜y＜0.005,0.001＜z＜0.01 o'clock, its luminous afterglow intensity is more than 400% of SrS:Eu material, and time of persistence is at (the minimum visual 0.32mcd/m of intelligent's eye more than 90 minutes
2), especially in the A component: La, Dy, Tm, Mn, the K Ag Na effect in the B component is remarkable, as:
SrS：Eu?Tm?K?????SrS：Eu?Tm?Ag
SrS：Eu?La?K?????SrS：Eu?La?Ag
SrS：Eu?Mn?K?????SrS：Eu?Mn?Ag
SrS：Eu?Tm?Na????SrS：Eu?Dy?Ag
There are two kinds of elements to mix simultaneously in addition among the A B significant effect is also arranged, as:
SrS：Eu?Dy?Mn?K?????SrS：Eu?Dy?Mn?Ag
SrS：Eu?Tm?La?K?????SrS：Eu?Tm?La?Ag
SrS：Eu?Tm?Dy?Na????SrS：Eu?Tm?Dy?K
SrS：Eu?Tm?Mn?K?Ag??SrS：Eu?Tm?Mn?K?Na
Two kinds of addings that element is above among A, the B simultaneously also produce effect
Work as M=Ca
0.5Sr
0.5Be Ca
0.5Sr
0.5This material of S:Eux Ay Bz mainly is orange red luminous, different along with the adding composition of A (Er Dy La Tm Y Mn) and B (Na K Ag) and concentration (x, y, z), its emission wavelength changes at 590-650nm, and glow color is yellow orange, orange, orange-red variation.
This material is than make Ca under identical conditions
0.5Sr
0.5S:Eu and Ca
0.05Sr
0.5Its luminous afterglow intensity of S:Eu A material significantly strengthens, and the time is elongated.By luminous relative afterglow measurement, can obviously find out its intensity and time of persistence relational expression Ca
0.5Sr
0.5S:Eu A B＞Ca
0.5Sr
0.5S:Eu A＞Ca
0.5Sr
0.5S:Eu, experiment shows 0.00005＜y＜0.05,0.00005 all there are influence in various degree, preferred 0.0002＜y＜0.02,0.0002＜z＜0.02 in＜z＜0.05,0.001＜y＜0.005 wherein, 0.001＜z＜0.01 is best, when 0.0001＜x＜0.001,0.001＜y＜0.005,0.001＜z＜0.01 o'clock, its luminous afterglow intensity is Ca
0.5Sr
0.5More than 300% of S:Eu material, time of persistence is at (the minimum visual 0.32mcd/m of intelligent's eye more than 60 minutes
2), especially Y, Tm, Mn in the A component, the Na Ag effect in the B component is remarkable, as: Ca
0.5Sr
0.5: Eu Tm Na Ca
0.5Sr
0.5: Eu Tm AgCa
0.5Sr
0.5: Eu Y Na Ca
0.5Sr
0.5: Eu Y Ag Ca
0.5Sr
0.5: Eu Mn Na Ca
0.5Sr
0.5: Eu Mn Ag
Two kinds of elements of A B add simultaneously in addition also significant effect, as: Ca
0.5Sr
0.5: Eu Tm Mn Na Ca
0.5Sr
0.5: Eu Tm Mn AgCa
0.5Sr
0.5: Eu Tm Y Na Ca
0.5Sr
0.5: Eu Tm Y AgCa
0.5Sr
0.5: Eu Tm Mn Na Ag Ca
0.5Sr
0.5: Eu Tm Mn Na K
Two kinds of addings that element is above among A, the B simultaneously also produce effect.
Work as M=Ca
1-nSr 0＜n＜1 is Ca
1-nThe glow color of its material of SrnS:Eux Ay Bz is red, orange, yellow rule and changes with the variation of n from 0-1, its luminous afterglow intensity and time, above-mentioned effect same is arranged.
When M represents Ca, Sr and composition thereof as mentioned above, wherein the 0-30% of mole number can be replaced by Ba or 0-50% can be replaced by Mg in the M composition, and above-mentioned effect same is also arranged.
The present invention also finds, for MS:Eux Ay Bz in the expression, M be selected from Ca, Mg, Sr, Ba one or more, A is selected from one kind of La, Y or two kinds, 0.02＜y＜2,0.0002＜z＜0.02 o'clock, the synthetic material is long-persistence luminous along with the change of Ca, Mg, Sr, Ba composition presents xanchromatic.When M=Sr, it is orange-yellow luminous that this system material is, Fig. 8 is emmission spectrum and the excitation spectrum when M=Sr A=La B=Na material, emmission spectrum is from the 550-700nm wideband spectrum, near the peak value 612nm, excitation spectrum is the continuous spectrum of 400nm-620nm, illustrates that this material all has absorption to visible light; When M=Ca, this system material takes on a red color long-persistence luminous, and visible light is also had very strong absorption; The structure of relevant this material is not clear at present.
Therefore, material of the present invention is from the proportioning of raw material element, and the performance of agglomerating processing method, product compared with prior art has outstanding characteristics.
This material can be used as a kind of pigment and is added in the various materials such as coating, printing ink, plastics, printing paste, makes various light emitting articles, in dark well red, orange or the long-persistence luminous effect of xanchromatic of presenting when unglazed at night.Fig. 1 (a) CaS:Eu, Er, the emmission spectrum of K material (b) CaS:Eu, Er, excitation spectrum Fig. 2 CaS:Eu of K material, Er, the luminous twilight sunset and time log-log coordinates (b) CaS:Eu of x-ray diffraction spectrogram Fig. 3 (a) CaS:Eu material of K material, the luminous twilight sunset of Er material and time log-log coordinates (c) CaS:Eu, Er, the luminous twilight sunset of K material and time log-log coordinates (d) CaS:Eu, Tm, Mn, the luminous twilight sunset of Na material and time log-log coordinates Fig. 4 (a) SrS:Eu, La, the emmission spectrum of K material (b) SrS:Eu, La, the luminous twilight sunset and time log-log coordinates (b) SrS:Eu of x-ray diffraction spectrogram Fig. 6 (a) SrS:Eu material of excitation spectrum Fig. 5 SrS Eu La K material of K material, the luminous twilight sunset of La material and time log-log coordinates
(c) the luminous twilight sunset of SrS:Eu, La, K material and time log-log coordinates
(d) the luminous twilight sunset of SrS:Eu, Mn, Tm, Na material and time log-log coordinates Fig. 7 (a) Ca
0.5Sr
0.5The emmission spectrum of S:Eu, Tm, Ag material
(b) Ca
0.5Sr
0.5Excitation spectrum Fig. 8 (a) Ca of S:Eu, Tm, Ag material
0.5Sr
0.5The luminous twilight sunset of S:Eu material and time log-log coordinates
(b) Ca
0.5Sr
0.5The luminous twilight sunset of S:Eu, Tm material and time log-log coordinates
(c) Ca
0.5Sr
0.5The luminous twilight sunset of S:Eu, Tm, Ag material and time log-log coordinates
(d) Ca
0.5Sr
0.5The luminous twilight sunset of S:Eu, Tm, Mn, Na material and time log-log coordinates Fig. 9 (a) are when M=Sr A=La B=Na x=0.0002 y=0.7 z=0.02
The emmission spectrum of synthetic materials
(b) when M=Sr A=La B=Na x=0.0002 y=0.7 z=0.02
The excitation spectrum of synthetic materials
Example 1 is as M=Ca A=Er B=Na x=0.0002 y=0.001, and during z=0.005, promptly CaS:Eu Er K material is synthetic:
Composition of raw materials (adopting carbonate to add carbon reduction) material name element mole number weight CaCO
31 100 gram S, 2.7 86.4 gram Eu
2O
30.0002 0.035 gram Er
2O
30.001 0.191 gram K
2S 0.005 0.275 gram NH
4Cl 0.02 1.07 gram CaF
20.095 1.2 gram C, 3 36 grams
With above-mentioned raw materials put into the agate mortar ground and mixed evenly after, in the corundum crucible of packing into, on mixing raw material, put into the carbon dusts of 36 grams, in 1150 ℃ of High Temperature Furnaces Heating Apparatuss during sintering 3, the cooling porphyrize, 100 eye mesh screens sieve, and promptly get example.
This material is behind radiation of visible light, move on to the dark place, present very strong red afterglow, survey its emmission spectrum and excitation spectrum with spectrograph, as shown in Figure 1, Fig. 1 (a) is the emmission spectrum under the 480nm excited by visible light, is the 580-720nm wideband spectrum, near the peak value 645nm, Fig. 1 (b) is the excitation spectrum at monitoring 645nm place, be the above wide band absorption of 400nm, this illustrates that this material all has absorption to visible light, through material is carried out the x-optical diffraction analysis.Confirm as the CaS structure, as shown in Figure 2.
For with the steady persistence of currently available products CaS:Eu relatively, that chooses example 1 does not add Er
2O
3And K
2The composition of raw materials of S prepares the CaS:Eu sample according to example 1 synthetic method.
Be similarly preparation CaS:Eu Er sample, that has chosen example 1 does not add K
2The proportioning raw materials of S and experimental technique.
By preceding chatting luminous afterglow measurement method, survey CaS:Eu, CaS:EuEr and CaS:Eu Er K twilight sunset relative value respectively, as shown in table 1.
Table 1
| Material | Luminous twilight sunset relative value 1 ' 3 ' 5 ' 8 ' 10 ' |
| ?CaS：Eu | ?10????4.1??2.9?????2?????1.6 |
| ?CaS：Eu、Er | ?26????8.4??6.7?????3.9???3.2 |
| ?CaS：Eu、Er、K | ?43????17???11.8????7.6???6.4 |
| ?CaS：Eu、Tm、Mn、Na | ?131???46???28.2????18.5??14.2 |
Press the value of table 1, draw luminous twilight sunset log-log coordinates Fig. 3 respectively, by a line, the decay curve of three kinds of materials is a straight line substantially, can find out obviously that from Fig. 3 the intensity of luminous twilight sunset and time sequence are CaS:Eu Er Na＞CaS:Eu Er＞CaS:Eu, this explanation is because the composition adding of Er K, make that CaS is the luminous twilight sunset enhancing of the material of matrix, time of persistence is elongated.
Change Er, K simultaneously and add the volumetric molar concentration amount, find that it all has influence in various degree at 0.00001-0.05 to the luminous afterglow intensity and time of this material, the volumetric molar concentration that therefore preferred Er, K add is 0.0002-0.02.
Example 2 is as M=Ca A=Tm Mn B=Na
x＝0.0001?y
Tm＝0.001，y
Mn＝0.002?z＝0.002
Composition of raw materials material name element mole number weight CaCO
31 100 gram S, 3.5 112 gram Eu
2O
30.00015 0.0264Tm
2O
30.001 0.193MnCO
30.002 0.206Na
2S 0.002 0.078SrF
20.03 3.768NH
4Cl 0.01 0.535
Its material synthesis method is with example 1, and obtained material takes on a red color long-persistence luminous, and its luminous twilight sunset relative intensity is as shown in table 1.
Example 3 is as M=Sr A=La B=K x=0.002 y=0.01 z=0.004
Be SrS:Eu La K
Composition of raw materials: (adopt vitriol to feed H
2Method) material name element mole number weight SrSO
41 183.6 gram Eu
2O
30.0002 0.035 gram La
2O
30.01 1.63 gram NH
4Cl 0.03 1.605 gram KCl 0.004 0.298 gram SrF
20.01 1.256 gram H
210 224 liters
With above-mentioned raw materials be placed on mix oven dry in the aqueous solution after, in the diamond spar crucible of packing into, insert in the sealing High Temperature Furnaces Heating Apparatus, feed H
21 liter/minute, when 1300 ℃ of sintering 4, the cooling porphyrize sieves through 100 eye mesh screens, gets product.
This material sample is after absorbing visible light, move on to the dark place, present very strong orange afterglow, survey its emmission spectrum and excitation spectrum with spectrograph, Fig. 4 (a) is the emmission spectrum under 480nm excites, be the 550-680nm wideband spectrum, near the peak value 612nm, Fig. 4 (b) is that the excitation spectrum at monitoring 612nm place is the above wide band absorption of 410nm, this illustrates that this material all has absorption to visible light, through sample is carried out the x-optical diffraction analysis, structure is SrS, as shown in Figure 5.
For with the steady persistence of currently available products SrS:Eu relatively, that chooses example 3 does not add La
2O
3With the composition of raw materials of KCl, prepared the SrS:Eu sample according to example 3 synthetic methods.
Be similarly preparation SrS:Eu La sample, chosen the proportioning raw materials that does not add KCl and the experimental technique of example 3.
By preceding chatting luminous afterglow measurement method, survey SrS:Eu, SrS:Eu La and SrS:Eu La K twilight sunset relative value respectively, as shown in table 2.
Table 2
| Material | Luminous twilight sunset relative value 1 ' 3 ' 5 ' 8 ' 10 ' |
| ?SrS：Eu | ?28?????12?????7.8????5.1??4 |
| ?SrS：Eu、La | ?60?????20.5???14?????9.2??7 |
| ?SrS：Eu、La、K | ?108????40.1???24?????15.3?11.8 |
| ?SrS：Eu、Y、Tm、Na | ?249????87?????50?????29???22.6 |
Press the value of table 2, draw luminous twilight sunset log-log coordinates Fig. 6 respectively, by a line, the decay curve of three kinds of materials is a straight line substantially, Fig. 6 can find out obviously that the intensity of luminous twilight sunset and time sequence are SrS:Eu La K＞SrS:Eu La＞SrS:Eu, and this explanation is because the composition adding of La K, make that CaS is the luminous twilight sunset enhancing of the material of matrix, time of persistence is elongated.
Change La, K simultaneously and add the volumetric molar concentration amount, find that it all has influence in various degree, the volumetric molar concentration 0.0002-0.02 that therefore preferred La K adds at 0.00001-0.05 to the afterglow intensity and time of this material.
It is SrS:Eu, Tm, Na that example 4 is worked as M=Sr A=Y, Tm B=Na
X=0.0003 y
Y=0.005 y
Tm=0.001 z=0.01 feed proportioning (adopts vitriol to feed NH
3Method) material name element mole number weight SrSO
41.2 220.3 gram Eu
2O
30.0003 0.0528 gram Tm
2O
30.001 0.193 gram Y
2O
30.005 0.565Na
2S 0.01 0.39 gram NH
4Cl 0.01 0.535 gram CaF
20.02 1.5 gram NH
312 268.8 grams
Its synthetic method is with example 3, and generated time is 5 hours, makes material and is orange-yellow luminous, and its luminous twilight sunset relative value is as shown in table 2.Example 5 is worked as M=Ca
0.5Sr
0.5A=Tm B=Ag
x＝0.0002?y＝0.002?z＝0.0015
Be Ca
0.5Sr
0.5S:Eu Tm Ag composition of raw materials (adopting carbonate to add the carbon method) material name element mole number weight CaCO
30.5 50 gram SrCO
30.5 73.8 gram S, 4 128Eu
2O
30.0002 0.035 gram Tm
2O
30.0002 0.386 gram AgNO
30.0015 0.255 gram NH
4Cl 0.03 1.605 gram CaF
20.01 0.78 gram C, 4.5 54 grams
With above-mentioned raw materials be placed on mix oven dry in the spirituous solution after, in the diamond spar crucible of packing into, on mixing raw material, put into 54 gram carbon dusts, 1200 ℃ of High Temperature Furnaces Heating Apparatus sintering 4 hours, the cooling porphyrize sieved through 100 screen clothes, gets product.
This material sample is after absorbing visible light, move on to the dark place, present very strong orange red luminous, survey its emmission spectrum and excitation spectrum with spectrograph, Fig. 7 (a) is the emmission spectrum under 480nm excites, and is the 550-700nm wideband spectrum, near the peak value 628nm, Fig. 7 (b) is the excitation spectrum at monitoring 628nm place, is the above wide band absorption of 400nm, and this illustrates that this material all has absorption to visible light.
For with currently available products Ca
0.5Sr
0.5The steady persistence of S:Eu relatively, that chooses example 5 does not add Tm
2O
3And AgNO
3Composition of raw materials, prepared Ca according to example 5 synthetic methods
0.5Sr
0.55The S:Eu sample.
Be similarly preparation Ca
0.5Sr
0.5S:Eu, Tm sample, that has chosen example 5 equally does not add AgNO
3Proportioning raw materials and experimental technique.
By preceding chatting luminous afterglow measurement method, survey Ca respectively
0.5Sr
0.5S:Eu, Ca
0.5Sr
0.5S:Eu, Tm and be Ca
0.5Sr
0.5S:Eu, Tm, Ag relative value, as shown in table 3.
Table 3
| Material | Luminous twilight sunset relative value 1 ' 3 ' 5 ' 8 ' 10 ' |
| ?Ca 0.5Sr 0.5S：Eu | ?24?????8????5.1??3.2??2.7 |
| ?Ca 0.5Sr 0.5S：Eu、Tm | ?39?????16.3?16.1?6.9??5.6 |
| ?Ca 0.5Sr 0.5S：Eu、Tm、Ag | ?69?????21.5?17.4?10.2?8.1 |
| ?Ca 0.5Sr 0.5S：Eu、Tm、Mn、Na | ?121????49???29.2?18.3?15.7 |
Press the value of table 3, draw luminous twilight sunset log-log coordinates Fig. 8 respectively, by a line, the decay curve of three kinds of materials is a straight line substantially, and Fig. 8 can find out obviously that the intensity of luminous twilight sunset and time sequence are Ca
0.5Sr
0.5S:Eu, Tm, Ag＞Ca
0.5OSr
0.5S:Eu, Tm＞Ca
0.5Sr
0.5S:Eu, this explanation makes Ca because the composition of Tm and Ag adds
0.5Sr
0.5S is that the luminous twilight sunset of the material of matrix strengthens, and time of persistence is elongated.
Change Tm, Ag simultaneously and add the volumetric molar concentration amount, find that it all has influence in various degree, the volumetric molar concentration 0.0002-0.02 that therefore preferred Tm, Ag add at 0.00001-0.05 to the afterglow intensity and time of this material.Example 6 is worked as M=Ca
0.5Sr
0.5A=Tm Mn B=Na
x＝0.0002?y
Tm＝0.001?y
Mn＝0.002?z＝0.002
Be Ca
0.5Sr
0.5S:Eu Tm Mn Na composition of raw materials (adopting carbonate to add the carbon method) material name element mole number weight CaCO
30.5 50 gram SrCO
30.5 73.8 gram S, 4.5 144 gram Eu
2O
30.0002 0.035 gram Tm
2O
30.001 0.193 gram Na
2S 0.002 0.078 gram NH
4Cl 0.03 1.605 gram MnCO
30.002 0.206 gram SrF
20.01 0.125 gram C, 4.5 54 grams
Its synthetic method makes material and is orange red luminous with example 5, and its luminous twilight sunset relative value is as shown in table 3.(employing vitriol feeds NH to example 7 when M=SrA=La B=Na x=0.0002 y=0.7 z=0.01 proportioning raw materials
3Method) material name element mole number weight SrSO
41 183.6 gram SrCO
30.1 14.76 gram La
2O
30.7 114.1 gram S, 3.2 102.4 gram Eu
2O
30.001 0.176 gram Na
2S 0.0020 0.156 gram NH
310 224 liters
This material experiment method is with example 4, make material behind radiation of visible light, present very strong orange-yellow luminous twilight sunset, its emmission spectrum and excitation spectrum are to excite down at 480nm (a) as shown in Figure 9, and emmission spectrum is the 550-680nm wideband spectrum, near the peak value 612nm, (b) be the excitation spectrum at monitoring 612nm place, be the above wide band absorption of 400nm, this illustrates that this material all has absorption to visible light.
Claims (9)
1. one kind is the long-afterglow photoluminescent of matrix with the metallic sulfide, it is characterized by to have following chemical constitution expression:
MS:Eux, Ay, Bz wherein M are selected from Ca, Sr, one or more mixtures of Mg, Ba;
A is selected from Er, Dy, La, Tm, one or more mixtures of Y, Mn;
B is selected from and is Na, K, one or more mixtures of Ag;
X, y, z are shared volumetric molar concentration, and x is 0.00001-0.005, and y is 0.0002-0.02, and z is 0.002-0.02.
2. long after glow luminous material as claimed in claim 1, it is characterized by M is that Ca is or/and Sr; A is selected from Er, La, Tm, Y, one or more mixtures of Mn; B is Na, K, one or more mixtures of Ag; X is 0.00001-0.005, and y is 0.0002-0.02, and z is 0.00002-0.02.
3. long after glow luminous material according to claim 1, its feature when A be La or/and during Y, y is 0.02-2.00.
4. as long after glow luminous material as described in the claim 2, it is characterized by that M is selected from Ca or/and Sr, and wherein mole number 0-30% can be replaced or 0-50% is replaced by Mg by Ba.
5. long after glow luminous material as claimed in claim 1 or 2 is characterized by CaS:Eux, Ay, Bz, and wherein A is selected from one kind of Er Tm Mn and multiple mixture thereof, and B is K, Ag and composition thereof; 0.0001＜x＜0.001,0.001＜y＜0.005,0.001＜z＜0.01.
6. long after glow luminous material as claimed in claim 1 or 2, it is characterized by SrS:Eux, Ay, Bz wherein A be selected from La, Tm, one kind of Mn and multiple mixture thereof, B is selected from Na, K, Ag and composition thereof.0.0001＜x＜0.001，0.001＜y＜0.005，0.001＜z＜0.01。
7. long after glow luminous material as claimed in claim 1 or 2 is characterized by (Ca
0.5Sr
0.5) S:Eux, Ay, Bz, wherein A is selected from Tm, Y, one kind of Mn and multiple mixture, and B is selected from Na, Ag and composition thereof 0.0001＜x＜0.001,0.001＜y＜0.005,0.001＜z＜0.01.
8. the manufacture method of long after glow luminous material as claimed in claim 1, the element mole proportioning that it is characterized by employed raw material is:
(1) carbonate adds the synthesis method of carbon
The element mole proportioning of its raw material that uses is:
M：1-1.5
S：1-5
Eu：0.00001-0.005
A：0.0002-0.02
B：0.0002-0.02
C:1-5NH
4Cl:0.01-0.2CaF
2Or/and SrF
2: 0.01-0.2;
(2) vitriol feeds H
2Or NH
3Or use carbon synthesis method
The element mole proportioning of its raw material that uses is;
M：1-1.5
S：0-5
Eu：0.00001-0.005
A：0.0002-0.02
B:0.0002-0.02H
2Or (2/3NH
3): 3-12 or C:1.5-6NH
4Cl:0.01-0.2CaF
2Or/and SrF
2: 0.01-0.2;
Its manufacturing process is: raw material is mixed, under reducing substances and the atmosphere under 900-1400 ℃, sintering 1-5 hour, through grind, sieving forms.
9. as the manufacture method of long persistence luminous sulfide material as described in the claim 8, it is characterized by describedly under reducing substances and atmosphere, be meant when the main raw material that forms matrix in synthetic is carbonate adding carbon; Form and feed H when the matrix main raw material is vitriol
2Or NH
3Or adding carbon.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111381A CN1091792C (en) | 1997-06-12 | 1997-06-12 | Long persistence luminous sulfide material and producing method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100368506C (en) * | 2001-08-31 | 2008-02-13 | 上海跃龙新材料股份有限公司 | Long-decay phosphor material and its prepn |
| CN100491496C (en) * | 2001-08-30 | 2009-05-27 | 双叶电子工业株式会社 | Fluorescent agent, preparation method for fluorescent layer and vacuum fluorescent display device |
| WO2012062066A1 (en) * | 2010-11-09 | 2012-05-18 | 四川新力光源有限公司 | Alternating current-driven led light emitting device |
| CN105713601A (en) * | 2016-03-31 | 2016-06-29 | 华南理工大学 | Near-infrared long-afterglow sulfide luminescent material as well as preparation method and application thereof |
| CN111826154A (en) * | 2019-04-22 | 2020-10-27 | 中国科学院福建物质结构研究所 | Preparation method of rare earth doped alkaline earth metal sulfide nano material |
| CN114479839A (en) * | 2022-02-23 | 2022-05-13 | 北京高压科学研究中心 | Multi-element rare earth sulfide luminescent material and preparation method thereof |
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| MY109224A (en) * | 1993-02-11 | 1996-12-31 | Samsung Display Devices Co Ltd | Mixed blue emitting phosphor. |
| CN1049915C (en) * | 1995-04-06 | 2000-03-01 | 中国科学院上海光学精密机械研究所 | Multifunctional optical material and component written in by UV, visible light and X ray and read out by IR |
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1997
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100491496C (en) * | 2001-08-30 | 2009-05-27 | 双叶电子工业株式会社 | Fluorescent agent, preparation method for fluorescent layer and vacuum fluorescent display device |
| CN100368506C (en) * | 2001-08-31 | 2008-02-13 | 上海跃龙新材料股份有限公司 | Long-decay phosphor material and its prepn |
| WO2012062066A1 (en) * | 2010-11-09 | 2012-05-18 | 四川新力光源有限公司 | Alternating current-driven led light emitting device |
| CN105713601A (en) * | 2016-03-31 | 2016-06-29 | 华南理工大学 | Near-infrared long-afterglow sulfide luminescent material as well as preparation method and application thereof |
| CN111826154A (en) * | 2019-04-22 | 2020-10-27 | 中国科学院福建物质结构研究所 | Preparation method of rare earth doped alkaline earth metal sulfide nano material |
| CN111826154B (en) * | 2019-04-22 | 2022-03-22 | 中国科学院福建物质结构研究所 | Preparation method of rare earth doped alkaline earth metal sulfide nano material |
| CN114479839A (en) * | 2022-02-23 | 2022-05-13 | 北京高压科学研究中心 | Multi-element rare earth sulfide luminescent material and preparation method thereof |
| CN114479839B (en) * | 2022-02-23 | 2023-09-19 | 北京高压科学研究中心 | Multi-element rare earth sulfide luminescent material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1091792C (en) | 2002-10-02 |
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