CN1062291C - Multifunctional efficient blue-green luminescent material and application thereof - Google Patents
Multifunctional efficient blue-green luminescent material and application thereof Download PDFInfo
- Publication number
- CN1062291C CN1062291C CN94112237A CN94112237A CN1062291C CN 1062291 C CN1062291 C CN 1062291C CN 94112237 A CN94112237 A CN 94112237A CN 94112237 A CN94112237 A CN 94112237A CN 1062291 C CN1062291 C CN 1062291C
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- CN
- China
- Prior art keywords
- alkaline earth
- luminescent material
- present
- green luminescent
- application
- Prior art date
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- Expired - Fee Related
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- 239000000463 material Substances 0.000 title claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012190 activator Substances 0.000 claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 19
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000004876 x-ray fluorescence Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- 229910052692 Dysprosium Inorganic materials 0.000 description 3
- 229910052775 Thulium Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000007777 multifunctional material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
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- Luminescent Compositions (AREA)
Abstract
The invention relates to a multifunctional high-efficiency blue-green luminescent material and application thereof. The matrix component is alkaline earth sulfide, wherein two impurity ions are doped, one is main activator copper; the other is a co-activator R, and in order to increase the luminous intensity and form ceramic, proper amounts of alkaline earth sulfate, alkaline earth fluoride and fluoride are added. The material of the present invention has the outstanding characteristics of multiple functions, wide application, capability of being used as a sensitive element of X rays, ultraviolet rays and infrared rays, an X-ray fluorescent screen, an anti-counterfeiting trademark or an anti-counterfeiting mark, high luminous efficiency, one screen which can be used for multiple times, and blue and green light emitted by the material is convenient for human eyes to observe.
Description
The present invention is blue green luminescent material of a kind of multifunctional efficient and application thereof.Material outstanding feature of the present invention is to have multiple function: (1). after ionizing rayss such as ultraviolet and X-ray excite, can produce strong blue green luminous; (2). after removing ultraviolet or X-ray source, blue green emitting can keep the long time (2-3 branch), and very strong, and in the dark luminous naked eyes can be distinguished; (3). if shine with the suitable infrared light of energy, then blue green emitting intensity can strengthen tens of times again after with ionization radiation irradiations such as ultraviolet and X-rays.
Material of the present invention can show and provide the judgement on orientation and the intensity if make a kind of X-radiation sensor with green glow to the X-ray that general X-ray machine produces;
Material of the present invention is if make a kind of x-ray fluorescence screen, and its high luminosity and steady persistence are suitable for the record and the processing of X-ray image;
Material of the present invention is if make a kind of infrared sensor, it can be efficiently with infrared light CO for example
2Laser converts blue green visible light at the infrared light of 10.6 μ m;
Material of the present invention also can be made a kind of anti-false trademark or anti-false mark.
Prior art:
Mix the II a-VI b compounds of group of rare earth, have good photoluminescence property.Has darker trap in these materials, trapped electron that can be stable, and just think just can cause photoluminescence that this phenomenon [is seen U.S. Pat 4806772 with the infrared sensing element that relevant material has been used to make the near infrared light response with near infrared light (λ ∠ 1.7 μ m); US4812659; US4812660].
But some adulterated alkaline earth sulfide has available photic and thermoluninescent characteristic simultaneously.Under special processing condition and chemical ingredients, on purpose in material, change composition, mix the trap of special impurity and some appropriate depth of introducing, strong X-ray and uv-radiation excitation luminescence can be made it not only to have but also under the effect of LONG WAVE INFRARED light and heat, the as seen luminous of suitable brightness can be produced.Thereby this material can have multiple use: as be used to detect the sensor of X-light, and X-light window of tube shows CO
2Laser is changed infrared sensing element in 10.6 μ m output, the infrared display screen of seeing spectrometer, infrared interferometer as conversion screen and do anti-false trademark etc.
Main purpose of the present invention provides a kind of multi-functional material that has, this material can produce strong blue green emitting after ionizing rayss such as ultraviolet and X-ray excite, after removing ultraviolet or X-ray source, blue green emitting can keep the long time (～2-3 branch), and very strong, in the dark can with the naked eye distinguish; And in the dark if shine with the suitable infrared light of energy, then blue green emitting can strengthen tens of times on former having powerful connections.
Both can make infrared sensor with material of the present invention, can make the X ray sensor again, XRF screen, ultraviolet-sensitive element, anti-false trademark or anti-false mark.And can encourage up-conversion luminescence with mid-infrared light.
Multifunctional material of the present invention is powder (piece) or the ceramic chip that is sintered into by multi-element compounds.Its matrix components is an alkaline earth sulfide, and main component is special impurity, the characteristics of luminescence of its decision material, and additive (alkaline-earth sulfate, alkali halide, alkali-earth halide etc.).Main matrix composition alkaline earth sulfide before not adding other composition, does not possess any available characteristic.Mix cupric ion into and obtained the characteristic of photoluminescence, and the mixing and the introducing of some defective under the special process condition of second kind of impurity (erbium, holmium, dysprosium and thulium), changed the characteristic of the photoluminescence of copper, increased twilight sunset and can encourage up-conversion luminescence with mid-infrared light.
The chemical ingredients of material of the present invention:
The main chemical compositions of element material therefor of the present invention is an alkaline earth sulfide, wherein be mixed with two kinds of foreign ions, a kind of dominant activator copper that is absolutely necessary, another kind is that auxilliary activator R can be a bait, holmium, thulium or dysprosium etc. add an amount of alkaline-earth sulfate, alkaline earth fluoride and alkali fluoride simultaneously so as to increasing luminous intensity and forming ceramic.Foreign ion can be an oxide compound, or vitriol or the adding of halid form.The weight percent ratio of its relative main matrix composition (SrS) is:
SrS 100 wt％
M
1(Ca，Sr，Ba)SO
4 0-10 wt％
M
1(Ca，Sr，Ba)F
2 0-8 wt％
M
2(Li，Na，K)F 0-7 wt％
CuSO
4 0.06-0.2 wt％
R(Er，Ho，Tm，Dy) 0-0.05 wt％
The preparation method of material of the present invention and functional element:
1. above-claimed cpd is weighed up by required ratio, be placed on behind the mixed grinding in the alumina crucible, in electric furnace, under inert atmosphere, heat, burnt 0.5-2 hour, promptly get material of the present invention after the cooling in 1000-1250 ℃ of temperature.
The above-mentioned material that makes grinds to form fine powder, sneaks in the tackiness agent (as polymer and resin etc.), applies at various thin slab substrate (as: papery, fiber, glass, quartz, aluminium flake, synthetic glass etc.) on, can be used as the X-radiation sensor behind the plastic packaging, or as certain x-ray fluorescence screen.
2. above-claimed cpd is weighed up mixing by required ratio, grind back press molding in the mould of various size and shape, be placed on afterwards in the electric furnace, under inert atmosphere, heat, burnt 0.5-2 hour in 1000-1250 ℃ of temperature, promptly get the ceramic chip of infrared sensor of the present invention after the cooling.
3. above-claimed cpd is weighed up by required ratio, be deposited on behind the mixed grinding on alpha-alumina crystals or the ceramic plate, be placed in the electric furnace, under inert atmosphere, heat, burnt 0.5-2 hour, promptly get infrared sensor of the present invention after the cooling in 1000-1250 ℃ of temperature.
Advantage of the present invention:
1. purposes is wide, as:
1) element of the present invention can be used for estimating the power and the orientation of X-light as the X-radiation sensor; With the Photodetection system combination, can survey the X-light intensity after the demarcation;
2) element of the present invention can be observed the image that X-light forms as the x-ray fluorescence screen, the brightness height, and twilight sunset is strong, is convenient to take a picture photoelectric recording and various image processing;
3) the present invention is used for observing CO as infrared sensor
2Deng infrared laser output, determine the orientation, spot size and disperse light beam parameters such as situation; Be used for as Analysis for CO
2Export the infrared wavelength display screen of seeing spectrometer of meticulous wavelength Deng infrared laser; Be used to be observation CO
2Deng screen of infrared laser interference image etc.;
4) material of the present invention also can be used for manufacturing certain anti-false trademark or stealthy sign indicating number (because it is essentially white).
2. material of the present invention is a white, and luminous be blue green, and approaching with the spectrum sensitivity district of human eye, thereby with the X-radiation sensor that it the is made visual observation that suits;
3. highly sensitive, twilight sunset is long, is beneficial to take a picture and photoelectric recording;
4. can wipe voluntarily in the fluoroscopic visual several minutes, thereby a screen can use many times;
Infrared sensor be make by inorganic ceramic material thereby good heat resistance, the physical strength height; And do not produce volatile matter, pollution-free;
6. infrared sensor has the highest sensitivity (to CO
210.6 μ m infrared laser is exported minimum detectable power～0.5W/cm
2);
Description of drawings:
Fig. 1. the luminescent spectrum distribution plan of material of the present invention (ordinate is a luminous intensity, and abscissa is a wavelength).
Embodiment:
Embodiment 1:
By the synthetic a kind of material of following composition, the weight percent ratio of its relative main matrix composition (SrS) is:
SrS 100 wt％
CaSO
4 5 wt％
CaF
2 3 wt％
CuSO
4 0.06 wt％
Tm
2O
3 0.05 wt％
The mixture that mixes after grinding well is placed in the alumina crucible according to the above ratio, burns 1 hour under 1050 ℃ of temperature, logical simultaneously argon gas.Can get the block of material of the present invention after the cooling.Its luminescent spectrum as shown in Figure 1.
The agglomerating block is ground to form fine powder, sneak in the tackiness agent (as polymer and resin etc.), apply on various thin slab substrate (as: papery, fiber, glass, quartz, aluminium flake, synthetic glass etc.), can be used as the X-radiation sensor behind the plastic packaging; As be coated on the transparent thin board substrate (as: glass, quartz, synthetic glass etc.), can be used as the x-ray fluorescence screen.
Prescription mixes the mixture after grinding well according to the above ratio, also can directly extrusion forming on demand in specific mould, under above-mentioned similarity condition, sinter heat-stable demonstration CO into
2The infrared conversion luminescence screen or the infrared sensor of laser.
Embodiment 2:
By a kind of material of following composition synthetic, wherein the weight percent ratio of the relative main matrix composition of each compound (SrS) is:
SrS 100 wt％
CaSO
4?3 wt％
SrSO
4?10 wt％
CaF
2 8 wt％
LiF 5 wt％
CuSO
4?0.12 wt％
Er
2O
30.02 wt％
The mixture extrusion forming (as sheet or bulk) that mixes after grinding well according to the above ratio is placed in the electric furnace then, burns 2 hours under 1000 ℃ of temperature, logical simultaneously argon gas.Can get heat-resisting infrared sensor of the present invention (ceramic plate) after the cooling.Its luminescent spectrum is shown in Fig. 1 curve.
Embodiment 3:
By the synthetic a kind of material of following composition, wherein the weight percent ratio of the relative main matrix composition of each compound (SrS) is:
SrS 100 wt％
CuSO
40.2 wt％
Mixture after mixing grinds well according to the above ratio is pressed into thin slice and is placed in the alumina crucible, heats in electric furnace under argon atmospher, burns 0.5 hour under 1250 ℃ of temperature, promptly gets the material of infrared sensor of the present invention after the cooling.Its luminescent spectrum is shown in Fig. 1 curve.
Utilize embodiment 1 described method that material is pulverized levigate sneaking into and make X-radiation sensor and steady persistence x-ray fluorescence screen in the bonding agent, respond well.
Claims (1)
1. blue green luminescent material, main component is an alkaline earth sulfide, wherein be mixed with two kinds of foreign ions, a kind of is dominant activator copper, another kind is auxilliary activator R, be to increase luminous intensity and form ceramic, add alkaline-earth sulfate, alkaline earth fluoride and fluorochemical, the weight percent that it is characterized in that forming the relative main matrix composition of the starting material component SrS of this blue green luminescent material is:
SrS 100 wt％
M
1SO
4 0-10 wt％
M
1F
2 0-8 wt％
M
2F 0-7 wt％
CuSO
4 0.06-0.2 wt％
R 0.02-0.05 wt％
Wherein: M
1Be Ca, or Sr, or Ba;
M
2Be Li, or Na, or K;
R is Er, or Tm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112237A CN1062291C (en) | 1994-07-21 | 1994-07-21 | Multifunctional efficient blue-green luminescent material and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94112237A CN1062291C (en) | 1994-07-21 | 1994-07-21 | Multifunctional efficient blue-green luminescent material and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1100131A CN1100131A (en) | 1995-03-15 |
| CN1062291C true CN1062291C (en) | 2001-02-21 |
Family
ID=5036028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94112237A Expired - Fee Related CN1062291C (en) | 1994-07-21 | 1994-07-21 | Multifunctional efficient blue-green luminescent material and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1062291C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB151830A (en) * | 1919-10-16 | 1920-10-07 | Benjamin Leaver | Improvements in sliding brackets, supports and the like |
| EP0057610A2 (en) * | 1981-02-02 | 1982-08-11 | Hitachi, Ltd. | Phosphors and processes for producing same |
| JPS61192788A (en) * | 1985-02-22 | 1986-08-27 | Mitsui Mining & Smelting Co Ltd | Long-afterglow blue phosphor |
-
1994
- 1994-07-21 CN CN94112237A patent/CN1062291C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB151830A (en) * | 1919-10-16 | 1920-10-07 | Benjamin Leaver | Improvements in sliding brackets, supports and the like |
| EP0057610A2 (en) * | 1981-02-02 | 1982-08-11 | Hitachi, Ltd. | Phosphors and processes for producing same |
| JPS61192788A (en) * | 1985-02-22 | 1986-08-27 | Mitsui Mining & Smelting Co Ltd | Long-afterglow blue phosphor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1100131A (en) | 1995-03-15 |
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