CN105347673A

CN105347673A - Tin-terbium co-doped luminescent glass having excitation wavelength broadened to deep ultraviolet region

Info

Publication number: CN105347673A
Application number: CN201510817051.8A
Authority: CN
Inventors: 李磊; 王洋; 王多金; 齐健; 夏凡舒; 陈国荣
Original assignee: East China University of Science and Technology
Current assignee: East China University of Science and Technology
Priority date: 2015-11-23
Filing date: 2015-11-23
Publication date: 2016-02-24

Abstract

Tin-terbium co-doped luminescent glass having an excitation wavelength broadened to a deep ultraviolet region is prepared by a melt cooling method at a certain temperature of T1 and annealing at a temperature of T2. The luminescent glass has luminescence centers of Tb<3+> and Sn<2+> under deep ultraviolet light excitation, a blue-green composite fluorescence is emitted, maximum emission peak values are respectively near 421 nm and 542 nm, and color coordinates can be adjusted by changing the Tb<3+>/Sn<2+> ratio; Sn<2+> is simultaneously used as a Tb<3+> deep ultraviolet excitation luminescent sensitizer, and the luminescence intensity at 542 nm is increased significantly; the luminescent center under near ultraviolet light excitation is Tb<3+>, and a green fluorescence with 542 nm as a main peak is emitted. The luminescent glass can meet requirements of laser devices and the like on insulation luminescent materials.

Description

The tin terbium that a kind of excitation wavelength is widened to dark purple outskirt mixes fluorescent glass altogether

Technical field

This invention fluorescent glass can be applied to deep ultraviolet and excite the field such as blue green light transmitting and near ultraviolet excitated green emission, large screen display (needing blue green light to construct total colouring), semi-conductor detection, fluorescence falsification preventing, laser medicine.

Background technology

In recent years, rare earth ion doped fluorescent glass has a wide range of applications in photoelectricity high-tech areas such as laser, optical amplifier, optical communication, energy storage and displays, and its preparation and performance are the important component parts of investigation of materials.Although correlative study has made great progress, also existing a series ofly has problem to be solved.As the research etc. of: the exploitation of New-type matrix material, the selection of rare earth ion and the determination of optimum doping concentration, the improvement of luminescent properties and regulation and control, luminescence mechanism.

Tb ³⁺as rare earth doped luminescent glass research in popular luminescent center ion, have luminous intensity high, the advantages such as the green fluorescence that monochromaticity is good and purity is high can be launched.But Tb ³⁺there is the weakness such as the more weak and absorption region of photoabsorption within the scope of deep ultraviolet is narrower.The tin terbium codoped phosphate host luminescent glass that the present invention studies, its composition expression formula is P ₂o ₅-SrO (RO)-SnO ₂-Tb(R is other divalent-metal ion, as Ba ²⁺, Ca ²⁺, Zn ²⁺).This glass remains Tb ³⁺the emission characteristic of ion under near ultraviolet excitation, excitation wavelength is expanded to dark purple outskirt simultaneously, and excites the luminous intensity at lower 542nm place than Tb in deep UV (ultraviolet light) ³⁺singly mix glass and have remarkable enhancing.In addition, can by adjustment Sn ²⁺/ Tb ³⁺luminescence under ratio makes its deep ultraviolet excite changes between blue light to green glow.

Summary of the invention

This invention relates to the phosphate luminescent glass that a kind of tin terbium is mixed altogether, and its chemical formula is: P ₂o ₅-SrO (RO)-SnO ₂-Tb(R is other divalent-metal ion, as Ba ²⁺, Ca ²⁺, Zn ²⁺).In order to obtain this fluorescent glass, the raw material used is compound (AR) NH respectively ₄h ₂pO ₄, SrCO ₃and/or RCO ₃(R is other divalent-metal ion, as Ba ²⁺, Ca ²⁺, Zn ²⁺), SnO ₂and Tb ₄o ₇(or Tb simple substance or other Tb compound).Preparation process is as follows:

1) according to the glass composition accurate weighing raw materials of compound of design, load weighted raw material is put into mortar and mixes, put into ceramic crucible, at about 1250 DEG C, found 2-3 hour;

2) raw material founded is cooled to glass in room temperature, puts into retort furnace and anneal.Annealing temperature is about 450 DEG C, and annealing time is 2-3 hour.Sample is down to room temperature with stove afterwards;

3) according to test request, sample is cut into sheet, surface finish process.

Fluorescent glass provided by the invention is under deep UV (ultraviolet light) excites, and blue-green fluorescent is obvious, and main emission peak is near 421nm and 542nm.Be green emission under near ultraviolet excitation, main emission peak is 542nm.

The invention has the advantages that:

1) fluorescent glass of the present invention can simultaneously by the near ultraviolet excitation of the deep UV (ultraviolet light) of 260-290nm and 300nm-400nm, and the former sends the blue green light of main emission peak at about 421nm and 542nm, and the latter sends with the green glow of 542nm for main emission peak;

2) the active ions Sn in fluorescent glass of the present invention ²⁺simultaneously as Tb ³⁺the sensitizing agent of ion deep ultraviolet stimulated luminescence, makes its 542nm luminescence enhancement;

3) fluorescent glass preparation technology of the present invention is simple, and easy handling, and stable chemical nature, be with a wide range of applications.

Accompanying drawing explanation

Fig. 1 is the excitation spectrum of fluorescent glass embodiment G1, G2 and G3 of the present invention.

Fig. 2 is the emmission spectrum of fluorescent glass embodiment G1, G2 and G3 of the present invention.

Embodiment

Embodiment G1:70P ₂o ₅-30SrO:2.0SnO ₂-0.2Tb

Preparation method: take primary ammonium phosphate (NH respectively ₄h ₂pO ₄) 37.0371g, Strontium carbonate powder (SrCO ₃) 10.1858g, tindioxide (SnO ₂) 0.6931g, terbium peroxide (Tb ₄o ₇) 0.0860g.Above-mentioned load weighted raw material is put into mortar and is mixed, and puts into ceramic crucible, at about 1250 DEG C, found 2-3h.At room temperature become glass shaping raw material after founding, then proceed in retort furnace and anneal.Annealing temperature is about 450 DEG C, annealing 2-3h.Sample furnace cooling is to room temperature afterwards.After cool to room temperature, by sample machine-shaping, polished finish is carried out on surface.The excitation spectrum (Fig. 1 a, b) that this fluorescent glass is monitored at 542nm and 488nm all shows, except retaining Tb ³⁺excitation peak outside, its excitation wavelength scope is expanded to dark purple outskirt, and intensity significantly strengthens.The emmission spectrum display at room temperature of this fluorescent glass, under 282nm excites, emmission spectrum is by the wider blue light of 350nm-500nm and combine with the green glow that 542nm is main emission peak that (a), wherein the latter is than Tb for Fig. 2 ³⁺singly mix glass and have remarkable enhancing; Under 375nm excites, then present and Tb ³⁺singly mix glass same take 542nm as the green emission (Fig. 2 b) of main peak.

Embodiment G2:70P ₂o ₅-30SrO:1.0SnO ₂-0.2Tb

Preparation method: take primary ammonium phosphate (NH respectively ₄h ₂pO ₄) 37.0371g, Strontium carbonate powder (SrCO ₃) 10.1858g, tindioxide (SnO ₂) 0.3464g, terbium peroxide (Tb ₄o ₇) 0.0860g.Above-mentioned load weighted raw material is put into mortar and is mixed, and puts into ceramic crucible, at about 1250 DEG C, found 2-3h.At room temperature become glass shaping raw material after founding, then proceed in retort furnace and anneal.Annealing temperature is about 450 DEG C, annealing 2-3h.Sample furnace cooling is to room temperature afterwards.After cool to room temperature, by sample machine-shaping, polished finish is carried out on surface.The excitation spectrum (Fig. 1 a, b) that this fluorescent glass is monitored at 542nm and 488nm is similar to embodiment 1, but intensity decreases.The emmission spectrum display at room temperature of this fluorescent glass, under 282nm excites, emmission spectrum is similar to embodiment 1, but luminous intensity is between G1 with singly mix Tb ³⁺between glass (Fig. 2 a), wherein with 542nm for the green glow of main transmitting and the strength ratio of blue light significantly improve; Under 375nm excites, then present and Tb ³⁺singly mix glass same take 542nm as the green emission (Fig. 2 b) of main peak.

Embodiment G3:70P ₂o ₅-30SrO:2.0SnO ₂-0.8Tb

Preparation method: take primary ammonium phosphate (NH respectively ₄h ₂pO ₄) 37.0371g, Strontium carbonate powder (SrCO ₃) 10.1858g, tindioxide (SnO ₂) 0.6931g, terbium peroxide (Tb ₄o ₇) 0.3440g.Above-mentioned load weighted raw material is put into mortar and is mixed, and puts into ceramic crucible, at about 1250 DEG C, found 2-3h.At room temperature become glass shaping raw material after founding, then proceed in retort furnace and anneal.Annealing temperature is about 450 DEG C, annealing 2-3h.Sample furnace cooling is to room temperature afterwards.After cool to room temperature, by sample machine-shaping, polished finish is carried out on surface.The excitation spectrum of this fluorescent glass is shown in accompanying drawing 1 (c, d), as seen from the figure, compared with embodiment 1, and the exciting light spectrogram feature similarity of embodiment 3 glass, but intensity all has raising by a relatively large margin.The emmission spectrum display at room temperature of this fluorescent glass, under 282nm excites, emission spectrum characteristics is similar to embodiment 1, but its luminous intensity within the scope of 350nm-480nm is weaker than embodiment 1(Fig. 2 c); Under 375nm excites, emission spectrum characteristics is similar to embodiment 1, but its intensity has raising (Fig. 2 d) by a relatively large margin.

Claims

1. the tin terbium that excitation wavelength is widened to dark purple outskirt mixes a fluorescent glass altogether, founds at T1 temperature, makes at T2 temperature after annealing; The matrix of this glass is phosphoric acid salt, and the luminescence center under deep UV (ultraviolet light) excites is Tb ³⁺and Sn ²⁺, Sn ²⁺simultaneously as the sensitizing agent of terbium ion luminescence, the luminescence center under near ultraviolet excitation is Tb ³⁺.

2. fluorescent glass as claimed in claim 1, it is characterized in that, this glass can by the deep ultraviolet of wavelength at 260nm-290nm and the near ultraviolet excitation of 300nm-400nm.

3. fluorescent glass as claimed in claim 1, is characterized in that, this fluorescent glass excites lower emission peak with the blue light that is peak value by 421nm in deep UV (ultraviolet light) and is that the green glow of peak value forms with 542nm; Under near ultraviolet excitation then with 542nm green glow for dominant emission peak.

4. fluorescent glass as claimed in claim 1, is characterized in that, active ions Sn in this fluorescent glass ²⁺make Tb as sensitizing agent simultaneously ³⁺the luminescence at lower 542nm place is excited to been significantly enhanced at deep ultraviolet.

5. the preparation method of fluorescent glass as claimed in claim 1, is characterized in that:

(1) primary ammonium phosphate of certain proportioning, Strontium carbonate powder (and/or other carbonate), terbium peroxide (or compound of terbium simple substance and other terbium) and tindioxide is taken by chemical formula;

(2) load weighted reagent grinds and Homogeneous phase mixing in ceramic mortar;

(3) sample mixed founds 2-3 hour at about 1250 DEG C, then at room temperature becomes glass;

(4) become the sample after glass to anneal at about 450 DEG C 2-3 hour, cool to room temperature with the furnace.