CN101870867B - Sulphide electron capture luminous material - Google Patents
Sulphide electron capture luminous material Download PDFInfo
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- CN101870867B CN101870867B CN201010214340A CN201010214340A CN101870867B CN 101870867 B CN101870867 B CN 101870867B CN 201010214340 A CN201010214340 A CN 201010214340A CN 201010214340 A CN201010214340 A CN 201010214340A CN 101870867 B CN101870867 B CN 101870867B
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Abstract
The invention discloses a sulphide electron capture luminous material, which comprises a ZnS substrate material, wherein main activating agents containing Pb and Cu acid compounds are added into the ZnS substrate material, at least one kind of co-activating agents containing Sm, Eu, Er, Yb and Mn acid compounds is added into the ZnS substrate material, the mixture is dried after being uniformly mixed, and high-temperature sintering is carried out in protective atmosphere. After ultraviolet ray absorption, the materials have momentary sunset glow, and can generate green light under the stimulation of infrared rays between 800 and 2000 nm. The electron capture luminous material of the invention can be used for detecting, tracking, checking and identifying invisible near infrared light. The invention can be widely applied to the multi-disciplinary technical fields such as near infrared laser detection, laser light spot display, optical fiber communication indication, optical information storage, X-ray image processing, infrared imaging and the like.
Description
Technical field
The invention belongs to infrared laser detecting and luminescent material applied technical field.
Background technology
Electron capture is luminous to be the recombination luminescence phenomenon that produces because of in electronics in the material and the hole transition process.
Existing electron capture luminous material is mainly barium fluochloride and the rare earth doped activator europium of strontium sulfide calcium; After the former absorbs the X ray energy; Release is luminous down in red laser irradiation, and it is good radioscopic image storage medium, but it can't realize the sensitive excitation luminescence to invisible near-infrared laser; Chinese patent 85100247,01142151.7 is to this existing announcement.The latter adds rare-earth activated dose of europium, samarium with strontium sulfide, sulfurated lime and is the main body; This luminescent material can sensitivity be realized the excitation luminescence to near-infrared laser; But its not enough place is prone to deliquescence; And stability and life-span are relatively poor, the preparation that in Chinese patent 200710023804.3,200610103418.0 grades, has disclosed its red illuminating material.When said material to little when having the luminous 808nm wavelength laser of red color visible and detecting; The reddish orange of himself sending luminous with exciting light in red light to mix be a place; Can't realize effective resolution; Practical ranges property receives very big restriction, like the commercially available prod trade mark HT582 of Shanghai Ke Run photoelectricity technology corporation, Ltd., HT612.
Existing in addition near-infrared laser is surveyed up-conversion luminescent material, is to be master's luminescent material with the rare-earth system material, and it has and excites and the narrow characteristics of emmission spectrum; Chinese patent 96122293.X, Chinese patent 01138927.3, Chinese patent 01138920.6; US5541012; US7648648 etc. have set forth its preparation method, and its not enough place can't realize extensive near infrared light wave band is surveyed, like commercially available prod trade mark HT111.
The luminescent material that with ZnS is matrix is the luminescent material of common widespread use; As: electroluminescent material, long afterglow luminous material, CRT luminescent material etc.; Usually near infrared light luminously has serious quenching effect, Chinese patent 96I21255.1,96247084.8 existing explanations to it.
To above problem, the present invention adds and contains Pb, Cu activator in the ZnS substrate material; Prepare electron capture luminous material through behind the high temperature sintering, it has satisfactory stability property, behind ultraviolet ray or radiation of visible light; It absorbs storage power, and keeps for a long time, after the infrared excitation irradiation; It is luminous that it produces HS release, realizes that invisible infrared rays is had high sensitivity detection, under infrared rays 800-2000nm excitation, produces green or orange luminescence.
The present invention has changed above-mentioned disadvantageous effect, and it is luminous that ZnS material itself can be produced through infrared excitation, has enlarged this material system range of application.
Electron capture luminous material of the present invention can be used for invisible near infrared light is surveyed, follows the tracks of, proofreads, discerned.Can be widely used in the material technical fields of learning such as near-infrared laser detection, laser facula demonstration, opticfiber communication indication, optical information storage, x-ray image processing, imagine infra-red more.
Summary of the invention
A kind of sulphide electron capture luminous material of the present invention, it comprises the ZnS substrate material, wherein adds the dominant activator that contains Pb, Cu acidic cpd; Add at least a coactivator that contains in Sm, Eu, Er, Yb, the Mn acidic cpd; The uniform mixing after drying, high temperature sintering in protective atmosphere is after this absorbed ultraviolet ray; Of short duration twilight sunset is arranged, under infrared rays 800-2000nm excitation, produce green emitting.
In the every gram weight of substrate material, the concentration of adding dominant activator Pb is 1X10 among the present invention
-2-5X10
-5, the concentration of Cu is 1X10
-3-1X10
-6, and the concentration of Pb should keep the concentration greater than Cu.The adding of Pb helps luminescent material to produce darker energy level, and keeps long-time stored energy, makes luminescent material can realize the near infrared light excitation luminescence to broad.
The present invention is in the every gram weight of substrate material, and the concentration of adding coactivator is 5X10
-3-1X10
-6The adding of coactivator can improve the sensitivity of luminescent material.
Acidic cpd is among the present invention: sulphate, nitrate compound, halogenide, phosphate cpd, acetic acid compound.Activator and coactivator adopt when containing the acidic anionic compound can be effectively and ZnS substrate material hybrid reaction.
Sintering temperature should be at the 800-1600 degree among the present invention; The crystallization phases height of ZnS luminescent material is at 1040 degree; The luminescent material that has superperformance among the present invention; Its ZnS microlitic structure is in a cube hexagonal mixed phase, and it has faint steady persistence and manifests, and it can have highly sensitive detection to the infrared light of 1600-2000nm.Protective atmosphere is a kind of in sulphur, nitrogen, the carbon reduction atmosphere, and protective atmosphere can prevent the luminescent material oxidation, improves luminous efficiency.
Electron capture luminous material of the present invention has faint steady persistence phenomenon, and it has essence different with ZnS class long-afterglow material, and latter's infrared light can produce quenching effect to luminous, and the former can produce strong enhancing promoter action to luminous by infrared light face.
During among the present invention in adding coactivator Sn, Mn one or more, and its concentration is greater than 1X10
-3The time, exciting down at infrared rays 800-130nm, the characteristic that can produce Sm, Mn is luminous, both yellow or orange luminescence.
Can add fusing assistant during the high temperature sintering high temperature sintering among the present invention, fusing assistant is the halogenide that contains Mg, Na, Ba, Li, K, and it can improve luminous intensity.Fusing assistant can reduce sintering temperature, improves the knot quality.Add-on is the 00.5-10% of substrate material weight.
Embodiment
A kind of sulphide electron capture luminous material of the present invention, it comprises the ZnS substrate material, wherein adds the dominant activator that contains Pb, Cu acidic cpd; Add at least a coactivator that contains in Sm, Eu, Er, Yb, the Mn acidic cpd; The uniform mixing after drying, high temperature sintering in protective atmosphere is after this absorbed ultraviolet ray; Of short duration twilight sunset is arranged, under infrared rays 800-2000nm excitation, produce green emitting.
In the every gram weight of substrate material, the concentration of adding dominant activator Pb is 1X10 among the present invention
-2-5x10
-5, the concentration of Cu is 1X10
-3-1X10
-6, and the concentration of Pb should keep the concentration greater than Cu.When the concentration of Pb during less than Cu, or only add Cu when not adding Pb, infrared light can produce quenching effect to the ZnS luminescent material.
The present invention adds coactivator in substrate material, coactivator contains a kind of in Sm, Eu, Er, Yb, the Mn acidic cpd at least, and the concentration that the every gram of substrate material adds coactivator is 5X10
-3-1X10
-5
Dominant activator and coactivator are to add with the acidic cpd form among the present invention, can be sulfate radical compound, nitrate radical compound, halogenide, phosphate compounds, acetate compound.As: copper sulfate, plumbic acetate, europium nitrate, Erbium trichloride etc.Above material adds the back and uses aqueous solution, and oven dry, and it can guarantee activator and the coactivator homogeneity in substrate material.
Sintering temperature should be at the 800-1600 degree among the present invention, and optimal sintering temperature is at the 950-1200 degree, and this temperature can make luminescent material that complete stable crystallization is arranged.Should and have under the protective atmosphere in anaerobic in the sintering and implement, protective atmosphere is a kind of in sulphur, nitrogen, the carbon reduction atmosphere; Wherein the protective atmosphere of sulfur-bearing can produce effect preferably to agglomerated material, promotes the raising of luminous intensity.Sintering time should remain on 1-5 hour.Use high-temperature electric resistance furnace to carry out when the present invention implements sintering, the material for preparing can be packed in the airtight silica tube or in the alumina crucible.
During among the present invention in adding coactivator Sm, Mn one or more, its concentration is greater than 1X10
-3The time, excite generation yellow or orange luminescence down at infrared rays 800-1300nm.When adding coactivator Sm, Mn concentration within the specific limits, it can produce the characteristic luminescent spectrum of Sm, Mn, and Sm shows yellow or orange luminescence usually, and Mn shows orange luminescence usually, and they can form with green mixes the broad band luminescent spectrum.
Can add fusing assistant during the high temperature sintering high temperature sintering among the present invention, fusing assistant is the halogenide that contains Mg, Na, Ba, Li, K, and add-on is the 0.5-10% of substrate material weight.As: lithium fluoride, sodium-chlor, Potassium Bromide etc.Fusing assistant can improve crystalline perfection, strengthens luminosity.
The present invention can add elemental sulfur in force in material, add-on is the 1-10% of substrate material weight, its can be when high temperature sintering protecting materials not oxidized.
The invention has the advantages that
1. a kind of sulphide electron capture luminous material of the present invention, it can produce luminous under infrared rays 800-2000nm excitation, especially can survey the infrared light of 1600-2000nm.
2.. the present invention produces the sulphide electron capture luminous material of luminous green under infrared excitation, can sensitively survey the 808nm wave band of laser, distinguishes original faint red visible light in the light source.
3.ZnS:Pb, the Cu luminescent material has satisfactory stability property, and serious moisture decomposing phenomenon can not take place, be more than 5 times of sulfurated lime material work-ing life.
4.ZnS luminescent material is common electroluminescent material, long afterglow luminous material, CRT luminescent material; Near infrared light has serious quenching effect to it; The present invention has changed above-mentioned disadvantageous effect, and it is luminous that ZnS material itself can be produced, and has enlarged material application system scope.
Electron capture luminous material of the present invention can be used for invisible near infrared light is surveyed, follows the tracks of, proofreads, discerned.Can be widely used in multidisciplinary technical fields such as near-infrared laser detection, laser facula demonstration, opticfiber communication indication, optical information storage, x-ray image processing, imagine infra-red.As: the infrared LED telepilot of using always in the household electrical appliances, YAG laser cutter, 1550nm opticfiber communication etc.
Embodiment 1
Get ZnS substrate material 30 grams, add plumbic acetate, add Pb content 8X10 in every relatively gram substrate material
-3Add copper sulfate, add Cu content 1x10 in every relatively gram substrate material
-1Add samaric nitrate, add Sm content 1X10 in every relatively gram substrate material
-1Add fusing assistant lithium fluoride 1 gram, add sulphur 1 gram.Water is mixed, oven dry under 120 degree.The exsiccant material is packed in the alumina crucible, seal; Sintering is 3 hours in 1100 degree electric furnaces, takes out cooling.
The material of present method preparation, at radiation of visible light after 10 seconds, place 3 little after, use infrared 1800nm light source irradiation excitation luminescence material, it can send bright green glow.
Embodiment 2
Get ZnS substrate material 1000 grams, add plumbic acetate, add Pb content 1X10 in every relatively gram substrate material
-3Add cupric nitrate, add Cu content 7x10 in every relatively gram substrate material
-5Add europium nitrate, add Eu content 5X10 in every relatively gram substrate material
-1Add fusing assistant sodium-chlor 20 grams, add sulphur 50 grams.Water is mixed, oven dry under 120 degree.The exsiccant material is packed in the alumina crucible, seal; Sintering is 4 hours in 1200 degree electric furnaces, takes out cooling.
The material of present method preparation, is placed after 0.2 hour after 2 seconds at UV-irradiation, uses infrared 808nm light source irradiation excitation luminescence material, and it can send bright green glow.
Embodiment 3
Get ZnS substrate material 100 grams, add plumbic acetate, add Pb content 5X10 in every relatively gram substrate material
-4Add cupric nitrate, add Cu content 1x10 in every relatively gram substrate material
-5Add samaric nitrate, add Sm content 1X10 in every relatively gram substrate material
-3Add manganous nitrate, add Mm content 1X10 in every relatively gram substrate material
-3Add fusing assistant Repone K 3 grams, add sulphur 5 grams.Water is mixed, oven dry under 120 degree.The exsiccant material is packed in the alumina crucible, seal; Sintering is 4 hours in 1200 degree electric furnaces, takes out cooling.
The material of present method preparation, is placed after 10 hours after 60 seconds at UV-irradiation, uses infrared 1064nm light source irradiation excitation luminescence material, and it can send bright orange coloured light.
After embodiment has been done to illustrate preferably to the present invention in the above; What should understand to one skilled in the art is; Under situation without departing from the spirit and scope of the present invention, to any change that the present invention did with improve all within the scope of the invention.
Claims (5)
1. sulphide electron capture luminous material, it comprises the ZnS substrate material, wherein adds the dominant activator that contains Pb, Cu acidic cpd; Add at least a coactivator that contains in Sm, Eu, Er, Yb, the Mn acidic cpd; The uniform mixing after drying, high temperature sintering in protective atmosphere is after this absorbed ultraviolet ray; Of short duration twilight sunset is arranged, under infrared rays 800-2000nm excitation, produce green emitting; In the every gram weight of substrate material, the concentration of adding dominant activator Pb is 1X10
-2-5X10
-5, the concentration of Cu is 1X10
-3-1X10
-6, and the concentration of Pb should keep the concentration greater than Cu; In the every gram weight of substrate material, the concentration of adding coactivator is 5X10
-3-1X10
-5
2. a kind of according to claim 1 sulphide electron capture luminous material, acidic cpd is: sulphate, nitrate compound, halogenide, phosphate cpd, acetic acid compound.
3. a kind of according to claim 1 sulphide electron capture luminous material, sintering temperature should be at the 800-1600 degree, and the substrate material crystalline structure is in cube-the hexagonal mixed phase; Protective atmosphere is a kind of in sulphur, nitrogen, the carbon reduction atmosphere.
4. when a kind of according to claim 1 sulphide electron capture luminous material, in adding coactivator Sm, Mn one or more, and its concentration is greater than 1X10
-3The time, excite generation yellow or orange luminescence down at infrared rays 800-1300nm.
5. a kind of according to claim 1 sulphide electron capture luminous material can add fusing assistant during high temperature sintering, and fusing assistant is the halogenide that contains Mg, Na, Ba, Li, K, and add-on is the 0.5-10% of substrate material weight, and it can improve luminous intensity.
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|---|---|---|---|
| CN201010214340A CN101870867B (en) | 2010-06-29 | 2010-06-29 | Sulphide electron capture luminous material |
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|---|---|---|---|
| CN201010214340A CN101870867B (en) | 2010-06-29 | 2010-06-29 | Sulphide electron capture luminous material |
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| CN101870867A CN101870867A (en) | 2010-10-27 |
| CN101870867B true CN101870867B (en) | 2012-10-03 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161892B (en) * | 2011-02-21 | 2013-07-10 | 上海洞舟实业有限公司 | Fluorescent material for X-ray memory imaging |
| CN103756672B (en) * | 2014-02-05 | 2016-03-16 | 上海科润光电技术有限公司 | A kind of green luminescent material and preparation detecting infrared laser |
| CN103756673B (en) * | 2014-02-05 | 2015-05-13 | 上海洞舟实业有限公司 | Blue luminescent material for infrared laser detection and preparation method |
| CN103759823B (en) * | 2014-02-05 | 2015-12-02 | 上海科润光电技术有限公司 | A kind of infrared laser detecting device |
| CN106117596A (en) * | 2016-06-28 | 2016-11-16 | 上海洞舟实业有限公司 | A kind of pressure Luminous tyre |
| CN106634971B (en) * | 2016-10-09 | 2019-04-05 | 上海洞舟实业有限公司 | A kind of highly sensitive X-ray detection luminescent material preparation |
| CN108410460A (en) * | 2018-06-04 | 2018-08-17 | 中建材蚌埠玻璃工业设计研究院有限公司 | A kind of preparation method of ZnS light-emitting films |
| CN113024103B (en) * | 2021-04-10 | 2022-08-26 | 南京至淳宏远科技有限公司 | Device and method for preparing rare earth doped optical fiber preform |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130689A (en) * | 2007-10-15 | 2008-02-27 | 彩虹集团电子股份有限公司 | Method of producing green fluorescent powder |
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| JP2004263068A (en) * | 2003-02-28 | 2004-09-24 | Toshiba Corp | Green light emitting fluorescent substance for low voltage/high current density use, and field emission type display unit using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101130689A (en) * | 2007-10-15 | 2008-02-27 | 彩虹集团电子股份有限公司 | Method of producing green fluorescent powder |
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Application publication date: 20101027 Assignee: Beijing Applied Biological Technologies Co., Ltd. Assignor: Shanghai Keyan Phosphor Technology Co., Ltd. Contract record no.: 2012220000044 Denomination of invention: Sulphide electron capture luminous material Granted publication date: 20121003 License type: Exclusive License Record date: 20121220 |
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