CN102492419A

CN102492419A - Preparation method for green light-excited long afterglow phosphor with warm color

Info

Publication number: CN102492419A
Application number: CN2011103548635A
Authority: CN
Inventors: 张尔攀; 孔哲; 席俊华; 季振国
Original assignee: Hangzhou Dianzi University
Current assignee: Hangzhou Dianzi University
Priority date: 2011-11-10
Filing date: 2011-11-10
Publication date: 2012-06-13
Anticipated expiration: 2031-11-10
Also published as: CN102492419B

Abstract

The invention relates to a preparation method for green light-excited long afterglow phosphor with warm color. All the conventional red phosphors are low in luminous intensity or short in afterglow time, or cause environment pollution, so that the practical requirements cannot be met. Through the adoption of the invention, red phosphor Ba2Zn1-xS3 : xMn2+ excited by green light is coated on the surface of green long afterglow phosphor SrAl2O4 : Eu2+, Dy3+; and the thickness of the red phosphor can be controlled, so as to realize the purpose of efficient warm color long afterglow radiating with green-olivine-yellow-orange-red lights. The preparation method solves the problem that the afterglow time of the conventional directly prepared red phosphors is short, thereby being a new way for preparing warm color long afterglow materials.

Description

The warm colour long after glow luminous material preparation method that a kind of green glow excites

Technical field

The present invention relates to luminescent material, relate in particular to long afterglow luminous material, is the warm colour long after glow luminous material preparation method that a kind of green glow excites.

Background technology

Long after glow luminous material is one type of important light-light-converting material and energy-storage economical material, and it can store luminous energy when rayed is arranged, and slow release again during no rayed is a kind of free of contamination cold light source.

Traditional long-afterglow material mainly is earth alkali metal and transition element sulfide, like CsS:Bi and ZnS:Cu etc.The poor chemical stability of this type material, after time lack, and need to add ri mostly.At present, material such as rare-earth ion activated sulfide, aluminate, silicate, titanate becomes the main body of new type long-persistence material.Up to now, surpassed 12 h the after time of green of being developed and blue long afterflow material, reached actual request for utilization, has been applied to a plurality of fields, and all kinds of noctilucence products are being brought into play greatest effect in Application Areas separately.

But, be all can't be equal to aspect luminosity or after time as the red illuminating material of one of three primary colours with materials such as green glow, blue lights, it also is in conceptual phase in the long after glow luminous material field.

Red illuminating material such as rare-earth ion activated alkaline earth sulfide are the red long afterglow luminous materials of the first-generation, but this system poor chemical stability, and the H that discharges of material deliquescence ₂S is an environmentally hazardous substance, adds that after time is short, and is also inadequate aspect practical; Titanates of alkali-earth metals, this type of luminescent material low lightness, can not reach application requiring after time; The red illuminating material of silicate substrate has good chemical and thermostability, and low in raw material cost is easy to get, and the application performance aspect luminescent ceramic is also fine, but after time is shorter; Rare-earth ion activated oxysulfide system has characteristics such as high brightness, thermotolerance and radioresistance are good, though increase to some extent than other type luminescent material after time, also far can not reach practical requirement; The green of aluminates system and the exploitation of blue emitting material are the most successful, and be slower but the research of its red long afterglow material then makes progress.

Summary of the invention

In view of the present all kinds of red illuminating materials of institute's primary study be not luminous intensity not high, be exactly after time too short, perhaps environment is had pollution, all can not reach practical requirement.Imagine compound steady persistence green luminescent material and red illuminating material; Utilize green long afterglow luminescent material to be light source activation emitting red light powder; Like this no matter whether the twilight sunset of red light-emitting material itself is enough long; As long as the green long afterglow material can send light, with its compound red illuminating material also can continue luminous, thereby reach red " steady persistence " luminous purpose.

Green and the red compound warm colour long after glow luminous material that obtains adopts the method for red illuminating material parcel green luminescent material to carry out compound.In this method, as long as red material parcel thickness is enough thick, red green material proportion is appropriate, and the light that the green light material that is wrapped sends can be absorbed by the red illuminating material of outside basically, obtains purer ruddiness thus.Through changing the parcel thickness of red material, can change emission wavelength to a great extent, can realize by green adjustable to red large span.But because green light material is wrapped in red material inside, how extraneous irradiates light gets into the green emitting core through red illuminating material is a difficult problem that needs solution.This can solve through selecting suitable red illuminating material, and promptly red illuminating material can absorb green effectively and send ruddiness, can let again the short wavelength light transmission it and excite inner green long afterglow material.

In sum, for the long after glow luminous material field, through green long afterglow material and red illuminating material can obtain can be from the green to the redness long-persistence luminous.Based on the great demand of existing market to long after glow luminous material, realize warm colour long-persistence luminous be an exploration that application prospect is arranged very much.The research of this type of warm colour " steady persistence " luminescent material does not appear in the newspapers at present as yet.

Preparing method's of the present invention basic step is following:

(1) BaO:ZnO:S is mixed than 2:1:3 with amount of substance, a certain amount of MnCO mixes ₃After mix described MnCO ₃Amount of substance be 0.01～0.1 of ZnO amount of substance.

(2) add SrAl ₂O ₄: Eu ²⁺, Dy ³⁺The green long afterglow luminescent powder, total mass and the SrAl of control BaO, ZnO and S ₂O ₄: Eu ²⁺, Dy ³⁺The ratio of quality be 20～10:1, thorough mixing is even, puts into the presintering of the program control atmosphere heat treatment stove of high temperature, the control sintering temperature is at 950 ℃, soaking time is 0.5h～1h.

(3) sample behind the sintering is put into vacuum system, vacuumize, make the pressure of Vakuumkammer be lower than 1 * 10 ^-1Pa.

(4) unlocking electronic rifle, the energy of electron beam are to regulate between 1KeV ~ 10KeV, and beam current density is at 10mAcm ^-2～100mAcm ^-2Between regulate.

(5) electron beam is scanned on sample,, make the warm colour long after glow luminous material up to sending macroscopic ruddiness.

Beneficial effect of the present invention: the luminescent powder composition that the packaging method that the present invention adopts obtains is even, and after time is longer than the warm colour luminescent material of directly preparation, can reach more than ten hours, and luminescent chromaticity is adjustable and character is more stable.

The present invention adopts the method for red illuminating material parcel green emitting powder, as long as the light that the green light material that is wrapped sends can be absorbed by the red illuminating material of outside basically, the interference of basically eliminate green light obtains purer ruddiness thus.Being equipped with the warm colour luminescent material with the traditional mixing legal system compares and obtains pure red light more.

Embodiment

Specify the present invention according to specific embodiment below, it is more obvious that the object of the invention and effect will become.

Embodiment 1:

(1) BaO:ZnO:S is mixed than 2:1:3 with amount of substance, a certain amount of MnCO mixes ₃Mix after (its amount of substance be ZnO amount of substance 0.01).

(2) add SrAl ₂O ₄: Eu ²⁺, Dy ³⁺The green long afterglow luminescent powder, control (1): the total mass ratio of (2) dry powder is 10:1, and thorough mixing is even, puts into the presintering of the program control atmosphere heat treatment stove of high temperature, and the control sintering temperature is at 950 ℃, and soaking time is 0.5h～1h.

(4) unlocking electronic rifle, the energy of electron beam are to regulate between 1KeV～10KeV, and beam current density is at 10mAcm ^-2～100mAcm ^-2Between regulate.

Embodiment 2:

(1) BaO:ZnO:S is mixed than 2:1:3 with amount of substance, a certain amount of MnCO mixes ₃Mix after (its amount of substance be ZnO amount of substance 0.05).

(2) add SrAl ₂O ₄: Eu ²⁺, Dy ³⁺The green long afterglow luminescent powder, control (1): the total mass ratio of (2) dry powder is 15:1, and thorough mixing is even, puts into the presintering of the program control atmosphere heat treatment stove of high temperature, and the control sintering temperature is at 950 ℃, and soaking time is 0.5h～1h.

Embodiment 3:

(1) BaO:ZnO:S is mixed than 2:1:3 with amount of substance, a certain amount of MnCO mixes ₃Mix after (its amount of substance be ZnO amount of substance 0.1).

(2) add SrAl ₂O ₄: Eu ²⁺, Dy ³⁺The green long afterglow luminescent powder, control (1): the total mass ratio of (2) dry powder is 20:1, and thorough mixing is even, puts into the presintering of the program control atmosphere heat treatment stove of high temperature, and the control sintering temperature is at 950 ℃, and soaking time is 0.5h～1h.

Claims

1. warm colour long after glow luminous material preparation method that green glow excites; It is characterized in that: red illuminating material that excites through green glow and green long afterglow luminescent material carry out compound, utilize green glow that long-acting the exciting of red illuminating material realized that the warm colour that red long-afterglow is luminous and colourity is adjustable is long-persistence luminous.

2. according to the described preparation method of claim 1, it is characterized in that the concrete steps of this method are following:

(1) BaO:ZnO:S is mixed than 2:1:3 with amount of substance, a certain amount of MnCO mixes ₃After mix described MnCO ₃Amount of substance be 0.01～0.1 of ZnO amount of substance;

(2) add SrAl ₂O ₄: Eu ²⁺, Dy ³⁺The green long afterglow luminescent powder, total mass and the SrAl of control BaO, ZnO and S ₂O ₄: Eu ²⁺, Dy ³⁺The ratio of quality be 20～10:1, thorough mixing is even, puts into the presintering of the program control atmosphere heat treatment stove of high temperature, the control sintering temperature is at 950 ℃, soaking time is 0.5h～1h;

(3) sample behind the sintering is put into vacuum system, vacuumize, make the pressure of Vakuumkammer be lower than 1 * 10 ^-1Pa;

(4) unlocking electronic rifle, the energy of electron beam are to regulate between 1KeV～10KeV, and beam current density is at 10mAcm ^-2～100mAcm ^-2Between regulate;