CN103666475A - Rare earth doped glass frequency conversion luminous material and preparation method thereof - Google Patents
Rare earth doped glass frequency conversion luminous material and preparation method thereof Download PDFInfo
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- CN103666475A CN103666475A CN201310668682.9A CN201310668682A CN103666475A CN 103666475 A CN103666475 A CN 103666475A CN 201310668682 A CN201310668682 A CN 201310668682A CN 103666475 A CN103666475 A CN 103666475A
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- 239000011521 glass Substances 0.000 title claims abstract description 148
- 239000000463 material Substances 0.000 title claims abstract description 72
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 title abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 238000005342 ion exchange Methods 0.000 claims abstract description 16
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 35
- 101710134784 Agnoprotein Proteins 0.000 claims description 24
- 238000000465 moulding Methods 0.000 claims description 22
- 238000007669 thermal treatment Methods 0.000 claims description 21
- 239000000156 glass melt Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 230000009466 transformation Effects 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 229910052745 lead Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- -1 rare earth ions Chemical class 0.000 abstract description 42
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 12
- 239000013081 microcrystal Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract 2
- 239000000919 ceramic Substances 0.000 abstract 1
- 239000005383 fluoride glass Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- 229910001961 silver nitrate Inorganic materials 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 27
- 230000035699 permeability Effects 0.000 description 18
- 239000000843 powder Substances 0.000 description 13
- 239000000146 host glass Substances 0.000 description 11
- 238000004020 luminiscence type Methods 0.000 description 11
- 239000002159 nanocrystal Substances 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 9
- 238000005086 pumping Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 238000004031 devitrification Methods 0.000 description 6
- 229910016036 BaF 2 Inorganic materials 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 229910005690 GdF 3 Inorganic materials 0.000 description 4
- 229910017768 LaF 3 Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910004261 CaF 2 Inorganic materials 0.000 description 3
- 229910016569 AlF 3 Inorganic materials 0.000 description 2
- 229910004573 CdF 2 Inorganic materials 0.000 description 2
- 229910016655 EuF 3 Inorganic materials 0.000 description 2
- 229910005269 GaF 3 Inorganic materials 0.000 description 2
- 229910005793 GeO 2 Inorganic materials 0.000 description 2
- 229910004379 HoF 3 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006066 glass batch Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Abstract
The invention discloses a rare earth doped glass frequency conversion luminous material and a preparation method thereof. The luminous material is formed by fluoride glass ceramics containing rare earth ions and silver nanoparticles. The preparation method comprises the steps of firstly preparing glass containing rare earth ions, secondly preparing the glass into the glass ceramics containing fluoride crystals through the heat treatment technology, and thirdly soaking the glass ceramics in a mixed salt melt containing silver nitrate to undergo ion exchange, thus obtaining the rare earth doped frequency conversion luminous material jointly enhanced by the silver nanoparticles and fluoride microcrystals. The obtained luminous material has the beneficial effects that the luminous material has good optical property and thermal stability; through irradiation of exciting light, by utilizing the local field enhancement effect of the silver nanoparticles, the rare earth ions in a low phonon energy environment created by the fluoride microcrystals achieve high frequency conversion luminous efficiency which can be maximally enhanced by 30 times, thus effectively making up for the problem of low rare earth ion doped glass frequency conversion luminous efficiency.
Description
Technical field
The invention provides a kind of rear-earth-doped glass frequency inverted luminescent material and preparation method, belong to frequency inverted luminescent material technical field.
Background technology
Rear-earth-doped frequency inverted luminescence technology has huge potential using value in fields such as solid-state laser, data storage, general illumination, 3 D stereo demonstration, micro-imaging, sensing technology, solar cell, anti-counterfeiting technology and military confrontations.Glass has following advantage aspect substrate material: the mixed concentration of rare earth in glass is higher, and the splitting of energy levels of rare earth ion and fluorescent emission exist inhomogeneous broadening phenomenon; The adjusting of matrix composition and pump light source range of choice are wide; Mature preparation process, cost is low etc.Therefore, take rear-earth-doped frequency inverted luminescent material that glass is matrix has met well at present low price, high-level efficiency, dominance energy, wavelength has been positioned to the demand in the application such as LASER Light Source of Infrared-Visible scope.
But, the rear-earth-doped frequency inverted luminescent material that the glass of take is matrix still faces a large amount of difficult problems aspect practical application, as: frequency inverted luminous efficiency is not high--the impact of the factor such as the incident light specific absorption that caused by host glass and rare earth ion oneself factor (as phonon energy, oscillator strength, specific refractory power and absorption cross section etc.) is low, multi-phonon relaxation rate is high and phonon energy is large; Tradition preparation technology lower frequency changes efficiency difficulty and improves--and major cause is that the factors such as rare earth ion energy level feature, doping content and glass matrix structural performance have a significant impact rare earth ion energy inter-stage cross relaxation rate, and the Effective Doping concentration that luminescence rare earth ion is made in host glass at traditional smelting process is difficult to be greatly improved.Above-mentioned factor has seriously restricted range of application and the prospect of such frequency inverted material.
In recent years, by thermal treatment presoma glass, the transparent glass ceramics that preparation comprises fluoride microcrystal, utilizes low phonon energy characteristic that crystal of fluoride possesses to improve the luminous efficiency of rare earth ion, has become a kind of effective means of improving rear-earth-doped glass luminescent properties.In addition, because the metal nanoparticles such as gold and silver and copper have unique surface effects, at present people have started this type of metal nanoparticle surface plasma resonance effect and the material characteristics of luminescence to combine and conduct a research.Combination about semiconductive luminescent materials and metal makes the research that luminous intensity improves just show effect.Therefore, silver nano-grain is combined with the frequency inverted glass material that comprises fluoride microcrystal, by the local field reinforcing effect of silver nano-grain and the low phonon energy characteristic of fluoride microcrystal, can be the efficient rear-earth-doped glass frequency inverted luminescent material of preparation new thinking and approach is provided.
Summary of the invention
The object of this invention is to provide a kind of rear-earth-doped glass frequency inverted luminescent material, this rear-earth-doped glass frequency inverted luminescent material is made by following raw material, and each raw material and molar percentage are: A
yo
x30～65 mol%, ZF
x10～45 mol %, R
yo
x0～40 mol%, Ln
yd
x0.01～10 mol%;
Wherein, x value be 1,2,3 or 5, y value be 1 or 2, A represent a kind of in Ge, Te, Si, P element, A
yo
xfor the mixed mixture in any proportion of one or more oxide compounds in the oxidation of Ge, Te, Si, P element; Z represents a kind of in Pb, Y, La, Ca, Sr, Ba, Gd, Al, Zn, Cd, K, Na element, ZF
xfor the mixed mixture in any proportion of one or more fluorochemicals in the fluorochemical of Pb, Y, La, Ca, Sr, Ba, Gd, Al, Zn, Cd, K, Na element; R represents a kind of in Pb, Y, La, Ca, Sr, Ba, Nb, Ga, Al, Gd, Zn, Ti, Sb, K, Na element, R
yo
xfor the mixed mixture in any proportion of one or more oxide compounds in the oxide compound of Pb, Y, La, Ca, Sr, Ba, Nb, Ga, Al, Gd, Zn, Ti, Sb, K, Na element; Ln represents a kind of in Yb, Er, Tm, Ho, Tb, Nd, Pr, Dy, Eu, Ce rare earth element; D represents a kind of in O, F element, Ln
yd
xfor the oxide compound of Yb, Er, Tm, Ho, Tb, Nd, Pr, Dy, Eu, Ce element, one or more oxide compounds in fluorochemical, fluorochemical mixed mixture in any proportion.
The preparation method who another object of the present invention is to provide above-mentioned rear-earth-doped glass frequency inverted luminescent material, comprises the steps:
(1) raw material is fully mixed, then at 900～1400 ℃, found 20～60 min and obtain glass melt, then glass melt is cast on the Stainless Molding Board that has been preheating to 200～350 ℃ fast, after moulding, at 20～50 ℃ of glass transformation temperatures lower than glass melt, be incubated 0.5～5 h, then the speed with 5～10 ℃/min is cooled to room temperature by temperature, obtain containing rare earth ion glass, and by prepared glass cut, mill and polished finish;
(2) by step (1) prepared containing rare earth ion glass below recrystallization temperature 50 ℃ to thermal treatment 1 ~ 36 h under the more than recrystallization temperature condition of 20 ℃, naturally cool to room temperature, obtain transparent glass-ceramics;
(3) by AgNO
3and NaNO
3mix, or AgNO
3and KNO
3after mixing, obtain mixing salt, the transparent glass-ceramics then step (2) being obtained is imbedded in mixing salt, then at 250～450 ℃, carries out ion-exchange 10 min～72 h and obtains the devitrified glass after ion-exchange, AgNO in mixing salt
3molar percentage be 0.5 ~ 30%, NaNO
3or KNO
3molar percentage be 70 ~ 99.5%;
(4) devitrified glass after ion-exchange is heat-treated to 0.5 h～72 h under containing the condition of 30 ℃～150 ℃ below the glass transformation temperature of rare earth ion glass step (1) is prepared, make to separate out in devitrified glass silver nano-grain, obtain containing the rare earth ion transparent glass-ceramics of silver nano-grain and fluoride microcrystal, i.e. rear-earth-doped glass frequency inverted luminescent material simultaneously.
Beneficial effect of the present invention is:
(1) rear-earth-doped glass frequency inverted luminescent material of the present invention has the low phonon energy environment of crystal of fluoride and the chemistry of oxide glass and mechanically stable characteristic concurrently;
(2) preparation method of the present invention can effectively control the particle size of argent and fluoride microcrystal, and the size that guarantees silver-colored particle and fluoride microcrystal is in nanoscale scope, makes made devitrified glass keep good light transmission;
(3) the present invention passes through excitation light irradiation, utilize the local field reinforcing effect of silver nano-grain, make the rare earth ion in low phonon energy environment realize high frequency inverted luminous efficiency, the enhancing of its luminous efficiency reaches as high as 30 times, has effectively made up the low problem of frequency inverted glass material luminous efficiency;
(4) the common Rare-earth Doped Luminescent Glass material strengthening of silver nano-grain of the present invention and fluoride microcrystal, is expected to prepare the commercial frequency changing luminous material that obtains efficient conversion pump energy.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but protection domain of the present invention is not limited to described content.
Embodiment 1
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material is with SiO
2, Na
2cO
3, ZnF
2, BaO, BaF
2, YbF
3and ErF
3for raw material makes, specifically comprise the steps:
By forming 44.5SiO
2-15Na
2o-5ZnF
2-10BaO-20BaF
2-5YbF
3-0.5ErF
3(mol%) take 10 grams of required SiO of total mass
2, Na
2cO
3, ZnF
2, BaO, BaF
2, YbF
3and ErF
3powder stock, after fully mixing, pack into be placed in crucible with cover and at 1400 ℃, found 45 min, then glass melt is cast on the Stainless Molding Board that has been preheating to 200 ℃ fast, after moulding, at the temperature lower than 30 ℃ of glass transformation temperatures, be incubated 1h, speed with 8 ℃/min is cooled to room temperature by temperature, obtain the glass containing rare earth ion, and by the prepared glass containing rare earth ion cut, mill and polished finish; The prepared glass containing rare earth ion, lower than thermal treatment 1 h at 20 ℃ of devitrification of glass temperature, is naturally cooled to room temperature, obtain containing BaF
2nanocrystalline rear-earth-doped devitrified glass; Prepared rear-earth-doped devitrified glass is imbedded to AgNO
3and NaNO
3mixing salt in, AgNO in mixing salt
3molar percentage be 0.5%, NaNO
3molar percentage be 99.5%, then at 250 ℃, carry out ion-exchange 72h, subsequently glass surface is cleaned, then lower than thermal treatment 72 h at 150 ℃ of host glass transition temperatures, obtains rear-earth-doped glass frequency inverted luminescent material.
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material has good light permeability, and in this material, the median size of barium fluoride crystallite is 10 nm, and the median size of Ag nano particle is about 36 nm, BaF
2nanocrystal and Ag nano particle being evenly distributed in glass, it is spherical and bar-shaped that Ag nano particle is, and this material has good light permeability in the visible-range of near infrared, at BaF
2under the acting in conjunction of nanocrystal and Ag nano particle, during 980 nm laser pumping, rare earth Up-conversion Intensity obtains approximately 8 times of overall enhanced.
Embodiment 2
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material is with TeO
2, GeO
2, K
2cO
3, PbO, PbF
2, CdF
2and TmF
3for raw material makes, specifically comprise the steps:
By forming 30TeO
2-20GeO
2-15K
2o-10PbO-10PbF
2-5CdF
2-10TmF
3(mol%) take 30 grams of required TeO of total mass
2, GeO
2, K
2cO
3, PbO, PbF
2, CdF
2and TmF
3powder stock, after fully mixing, pack into be placed in crucible with cover and at 950 ℃, found 10 min, then glass melt is cast on the Stainless Molding Board that has been preheating to 200 ℃ fast, after moulding, at the temperature lower than 20 ℃ of glass transformation temperatures, be incubated 0.5 h, speed with 5 ℃/min is cooled to room temperature by temperature, obtain the glass containing rare earth ion, and by the prepared glass containing rare earth ion cut, mill and polished finish; The prepared glass containing rare earth ion, lower than thermal treatment 20 h at 40 ℃ of devitrification of glass temperature, is naturally cooled to room temperature, obtain containing PbF
2nanocrystalline rear-earth-doped devitrified glass; Prepared rear-earth-doped devitrified glass is imbedded to AgNO
3and KNO
3mixing salt in, AgNO in mixing salt
3molar percentage be 1%, KNO
3molar percentage be 99%, then at 300 ℃, carry out ion-exchange 48 h, subsequently glass surface is cleaned, then lower than thermal treatment 48 h at 50 ℃ of host glass transition temperatures, obtains rear-earth-doped glass frequency inverted luminescent material.
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material has good light permeability, PbF in material
2the median size of crystallite is about 18 nm, and the median size of Ag nano particle is about 22 nm, PbF
2nanocrystal and Ag nano particle being evenly distributed in glass, it is spherical and bar-shaped that Ag nano particle is, and this material has good light permeability in the visible-range of near infrared, under 800 nm laser pumpings, conversion luminescence luminous intensity is whole on the whole improves 15 times.
Embodiment 3
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material is with SiO
2, Al
2o
3, NaF, Gd
2o
3, GdF
3, TbF
3and Tb
2o
3for raw material makes, specifically comprise the steps:
By forming 44SiO
2-17Al
2o
3-17NaF-10Gd
2o
3-10.5GdF
3-1TbF
3-0.5Tb
2o
3(mol%) take 10 grams of required SiO of total mass
2, Al
2o
3, NaF, Gd
2o
3, GdF
3, TbF
3and Tb
2o
3powder stock, after fully mixing, pack into be placed in crucible with cover and at 1350 ℃, found 50 min, then glass melt is cast on the Stainless Molding Board that has been preheating to 280 ℃ fast, after moulding, at the temperature lower than 35 ℃ of glass transformation temperatures, be incubated 5 h, speed with 10 ℃/min is cooled to room temperature by temperature, obtain the glass containing rare earth ion, and by the prepared glass containing rare earth ion cut, mill and polished finish; The prepared glass containing rare earth ion, lower than thermal treatment 2h at 25 ℃ of devitrification of glass temperature, is naturally cooled to room temperature, obtain containing GdF
3nanocrystalline rear-earth-doped devitrified glass, imbeds AgNO by prepared rear-earth-doped devitrified glass
3and NaNO
3mixing salt in, AgNO in mixing salt
3molar percentage be 10%, NaNO
3molar percentage be 90%, then at 350 ℃, carry out ion-exchange 0.5h, subsequently glass surface is cleaned, then lower than thermal treatment 12h at 50 ℃ of host glass transition temperatures, obtains rear-earth-doped glass frequency inverted luminescent material.
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material has good light permeability, GdF in this material
3the median size of crystallite is about 20 nm, and the median size of Ag nano particle is about 16 nm, GdF
3nanocrystal and Ag nano particle being evenly distributed in glass, Ag nano particle is spherical, and this material has good light permeability in the visible-range of near infrared, and under 275 nm laser pumpings, whole lower conversion luminescence luminous intensity is whole improves 14 times.
Embodiment 4
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material is with SiO
2, Al
2o
3, KF, CaCO
3, CaF
2, Nd
2o
3and HoF
3for raw material makes, specifically comprise the steps:
By forming 35SiO
2-10Al
2o
3-20KF-7CaO-25CaF
2-Nd
2o
3-2HoF
3(mol%) take 10 grams of required SiO of total mass
2, Al
2o
3, KF, CaCO
3, CaF
2, Nd
2o
3and HoF
3powder stock, after fully mixing, pack in crucible with cover and be placed at 1350 ℃ and found 60min, then glass melt is cast on the Stainless Molding Board that has been preheating to 280 ℃ fast, after moulding, at the temperature lower than 50 ℃ of glass transformation temperatures, be incubated 8 h, speed with 5 ℃/min is cooled to room temperature by temperature, obtain the glass containing rare earth ion, and by the prepared glass containing rare earth ion cut, mill and polished finish; By the prepared glass containing rare earth ion thermal treatment 8h under lower than devitrification of glass temperature 50 C, naturally cool to room temperature, obtain, containing the nanocrystalline rear-earth-doped devitrified glass of CaF, prepared rear-earth-doped devitrified glass being imbedded to AgNO
3and KNO
3mixing salt in, AgNO in mixing salt
3molar percentage be 30%, KNO
3molar percentage be 70%, then at 350 ℃, carry out ion-exchange 10 min, subsequently glass surface is cleaned, then lower than thermal treatment 2h at 30 ℃ of host glass transition temperatures, obtains rear-earth-doped glass frequency inverted luminescent material.
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material has good light permeability, CaF in this material
2the median size of crystallite is about 36 nm, and the median size of Ag nano particle is about 6 nm, CaF
2nanocrystal and Ag nano particle being evenly distributed in glass, Ag nano particle is spherical, and this material has good light permeability in the visible-range of near infrared, and under 800 nm laser pumpings, conversion luminescence luminous intensity is whole on the whole improves 7 times.
Embodiment 5
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material is with SiO
2, Y
2o
3, YF
3, K
2cO
3, La
2o
3, Sb
2o
3and DyF
3for raw material makes, specifically comprise the steps:
By forming 58SiO
2-10Y
2o
3-15YF
3-13K
2o-3La
2o
3-1Sb
2o
3-DyF
3(mol%) take 15 grams of required SiO of total mass
2, Y
2o
3, YF
3, K
2cO
3, La
2o
3, Sb
2o
3and DyF
3powder stock, after fully mixing, pack in crucible with cover and be placed at 1300 ℃ and found 60min, then glass melt is cast on the Stainless Molding Board that has been preheating to 2800 ℃ fast, after moulding, at the temperature lower than 50 ℃ of glass transformation temperatures, be incubated 5h, speed with 8 ℃/min is cooled to room temperature by temperature, obtain the glass containing rare earth ion, and by the prepared glass containing rare earth ion cut, mill and polished finish; By the prepared glass containing rare earth ion thermal treatment 8h under the condition of 20 ℃ below recrystallization temperature, naturally cool to room temperature, obtain containing YF
3nanocrystalline rear-earth-doped devitrified glass, imbeds AgNO by prepared rear-earth-doped devitrified glass
3and KNO
3mixing salt in, AgNO in mixing salt
3molar percentage be 5%, KNO
3molar percentage be 95%, then at 350 ℃, carry out ion-exchange 30 min, subsequently glass surface is cleaned, then lower than thermal treatment 8 h at 50 ℃ of host glass transition temperatures, obtains rear-earth-doped glass frequency inverted luminescent material.
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material has good light permeability, YF in this material
3the median size of crystallite is about 11 nm, and the median size of Ag nano particle is about 9 nm, YF
3nanocrystal and Ag nano particle being evenly distributed in glass, Ag nano particle is spherical, and this material has good light permeability in the visible-range of near infrared, and under 457.9 nm laser pumpings, whole lower conversion luminescence luminous intensity is whole improves 6 times.
Embodiment 6
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material is with SiO
2, NaF, SrF
2, AlF
3and PrF
3powder is that raw material makes, and specifically comprises the steps:
By forming 65SiO
2-20NaF-10SrF
2-2AlF
3-3PrF
3(mol%) take 15 grams of required SiO of total mass
2, NaF, SrF
2, AlF
3and PrF
3powder stock, after fully mixing, pack into be placed in crucible with cover and at 1000 ℃, found 55 min, then glass melt is cast on the Stainless Molding Board that has been preheating to 280 ℃ fast, after moulding, at the temperature lower than 50 ℃ of glass transformation temperatures, be incubated 5h, speed with 8 ℃/min is cooled to room temperature by temperature, obtain the glass containing rare earth ion, and by the prepared glass containing rare earth ion cut, mill and polished finish; By the prepared glass containing rare earth ion thermal treatment 6h under the condition of 10 ℃ below recrystallization temperature, obtain containing SrF
2nanocrystalline rear-earth-doped devitrified glass, imbeds AgNO by prepared rear-earth-doped devitrified glass
3and NaNO
3mixing salt in, AgNO in mixing salt
3molar percentage be 3%, NaNO
3molar percentage be 97%, then at 350 ℃, carry out ion-exchange 2h, subsequently glass surface is cleaned, then lower than thermal treatment 36h at 110 ℃ of host glass transition temperatures, obtains rear-earth-doped glass frequency inverted luminescent material.
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material has good light permeability, SrF in this material
2the median size of crystallite is about 10 nm, and the median size of Ag nano particle is about 2 nm, SrF
2nanocrystal and Ag nano particle being evenly distributed in glass, it is spherical and bar-shaped that Ag nano particle is, and this material has good light permeability in the visible-range of near infrared, under 475.9 nm laser pumpings, whole lower conversion luminescence luminous intensity is whole improves 6 times.
Embodiment 7
Rear-earth-doped glass frequency inverted luminescent material TeO described in the present embodiment
2, ZnO, Na
2cO
3, Nb
2o
5, La
2o
3, LaF
3and EuF
3powder is that raw material makes, and specifically comprises the steps:
By forming 47.99TeO
2-7ZnO-18Na
2o-10Nb
2o
5-5La
2o
3-12LaF
3-0.01EuF
3(mol%) take 15 grams of required TeO of total mass
2, ZnO, Na
2cO
3, Nb
2o
5, La
2o
3, LaF
3and EuF
3powder stock, after fully mixing, pack into be placed in crucible with cover and at 900 ℃, found 30 min, then glass melt is cast on the Stainless Molding Board that has been preheating to 200 ℃ fast, after moulding, at the temperature lower than 30 ℃ of glass transformation temperatures, be incubated 5h, speed with 8 ℃/min is annealed to room temperature, obtain the glass containing rare earth ion, and by the prepared glass containing rare earth ion cut, mill and polished finish; By the prepared glass containing rare earth ion thermal treatment 8h under the condition of 5 ℃ below recrystallization temperature, naturally cool to room temperature, obtain containing LaF
3nanocrystalline rear-earth-doped devitrified glass, imbeds AgNO by prepared rear-earth-doped devitrified glass
3and NaNO
3mixing salt in, AgNO in mixing salt
3molar percentage be 5%, NaNO
3molar percentage be 95%, then at 350 ℃, carry out ion-exchange 20min, subsequently glass surface is cleaned, then below lower than host glass transition temperature thermal treatment 3h in the scope of 70 ℃, obtain rear-earth-doped glass frequency inverted luminescent material.
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material has good light permeability, LaF in this material
3the median size of crystallite is about 4nm, LaF
3nanocrystal and Ag nano particle being evenly distributed in glass, Ag nano particle is spherical, and this material has good light permeability in the visible-range of near infrared.Under 468 nm laser pumpings, whole lower conversion luminescence luminous intensity is whole improves approximately 17 times.
Embodiment 8
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material is with TeO
2, TiO
2, KF and PbF
2powder is that raw material makes, and specifically comprises the steps:
By forming 55TeO
2-10TiO
2-10KF-25PbF
2(mol%) take 15 grams of required TeO of total mass
2, TiO
2, KF and PbF
2powder stock, adds CeF by 0.01 mol% of glass batch
3after fully mixing, pack in crucible with cover and be placed at 900 ℃ and found 20min, then glass melt is cast on the Stainless Molding Board that has been preheating to 200 ℃ fast, after moulding, at the temperature lower than 30 ℃ of glass transformation temperatures, be incubated 5h, speed with 8 ℃/min is annealed to room temperature, obtain the glass containing rare earth ion, and by the prepared glass containing rare earth ion cut, mill and polished finish; By prepared glass thermal treatment 6h at devitrification of glass temperature containing rare earth ion, naturally cool to room temperature, obtain containing PbF
2nanocrystalline rear-earth-doped devitrified glass, imbeds AgNO by prepared rear-earth-doped devitrified glass
3and KNO
3mixing salt in, AgNO in mixing salt
3molar percentage be 5%, KNO
3molar percentage be 95%, then at 400 ℃, carry out ion-exchange 2h, subsequently glass surface is cleaned, then lower than thermal treatment 24 h at 130 ℃ of host glass transition temperatures.
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material has good light permeability, PbF in this material
2the median size of crystallite is about 22 nm, and the median size of Ag nano particle is about 10 nm, PbF
2nanocrystal and Ag nano particle being evenly distributed in glass, it is spherical and bar-shaped that Ag nano particle is, and this material has good light permeability in the visible-range of near infrared, under 800 nm laser pumpings, conversion luminescence luminous intensity is whole on the whole improves approximately 25 times.
Embodiment 9
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material is with P
2o
5, Na
2cO
3, Nb
2o
5, PbF
2and GaF
3powder is that raw material makes, and specifically comprises the steps:
By forming 30P
2o
5-20Na
2o-10K
2o-5Nb
2o
5-25PbF
2-10GaF
3(mol%) take 15 grams of required P of total mass
2o
5, Na
2cO
3, K
2cO
3, Nb
2o
5, PbF
2and GaF
3powder stock, adds Er by 10 mol% of glass batch
2o
3after fully mixing, pack in crucible with cover and be placed at 1150 ℃ and found 30min, then glass melt is cast on the Stainless Molding Board that has been preheating to 250 ℃ fast, after moulding, at the temperature lower than 30 ℃ of glass transformation temperatures, be incubated 5 h, speed with 8 ℃/min is annealed to room temperature, obtain the glass containing rare earth ion, and by the prepared glass containing rare earth ion cut, mill and polished finish; The prepared glass containing rare earth ion, higher than thermal treatment 4h at 10 ℃ of devitrification of glass temperature, is naturally cooled to room temperature, obtain containing PbF
2nanocrystalline rear-earth-doped devitrified glass, imbeds AgNO by prepared rear-earth-doped devitrified glass
3and K
2cO
3, NaNO
3mixing salt in, AgNO in mixing salt
3molar percentage be 7%, NaNO
3molar percentage be 60%, K
2cO
3molar percentage be 33%, then at 400 ℃, carry out ion-exchange 2h, subsequently glass surface is cleaned, then lower than thermal treatment 0.5 h at 30 ℃ of host glass transition temperatures.
Described in the present embodiment, rear-earth-doped glass frequency inverted luminescent material has good light permeability, PbF in this material
2the median size of crystallite is about 19 nm, and the median size of Ag nano particle is about 2 nm, PbF
2nanocrystal and Ag nano particle being evenly distributed in glass, it is spherical and bar-shaped that Ag nano particle is, and this material has good light permeability in the visible-range of near infrared, under 800 nm laser pumpings, conversion luminescence luminous intensity is whole on the whole improves approximately 30 times.
Claims (2)
1. a rear-earth-doped glass frequency inverted luminescent material, is characterized in that this rear-earth-doped glass frequency inverted luminescent material is made by following raw material, and each raw material and molar percentage are: A
yo
x30～65 mol%, ZF
x10～45 mol %, R
yo
x0～40 mol%, Ln
yd
x0.01～10 mol%;
Wherein, x value be 1,2,3 or 5, y value be 1 or 2, A represent a kind of in Ge, Te, Si, P element, A
yo
xfor one or more in the oxidation of Ge, Te, Si, P element; Z represents a kind of in Pb, Y, La, Ca, Sr, Ba, Gd, Al, Zn, Cd, K, Na element, ZF
xfor one or more in the fluorochemical of Pb, Y, La, Ca, Sr, Ba, Gd, Al, Zn, Cd, K, Na element; R represents a kind of in Pb, Y, La, Ca, Sr, Ba, Nb, Ga, Al, Gd, Zn, Ti, Sb, K, Na element, R
yo
xfor one or more in the oxide compound of Pb, Y, La, Ca, Sr, Ba, Nb, Ga, Al, Gd, Zn, Ti, Sb, K, Na element; Ln represents a kind of in Yb, Er, Tm, Ho, Tb, Nd, Pr, Dy, Eu, Ce rare earth element; D represents a kind of in O, F element, Ln
yd
xfor the oxide compound of Yb, Er, Tm, Ho, Tb, Nd, Pr, Dy, Eu, Ce element or one or more in fluorochemical.
2. the preparation method of rear-earth-doped glass frequency inverted luminescent material claimed in claim 1, is characterized in that comprising the steps:
(1) raw material is fully mixed, then at 900～1400 ℃, found 20～60 min and obtain glass melt, then glass melt is cast on the Stainless Molding Board that has been preheating to 200～350 ℃ fast, after moulding, at 20～50 ℃ of glass transformation temperatures lower than glass melt, be incubated 0.5～5 h, then the speed with 5～10 ℃/min is cooled to room temperature by temperature, obtain containing rare earth ion glass, and by prepared glass cut, mill and polished finish;
(2) by step (1) prepared containing rare earth ion glass below recrystallization temperature 50 ℃ to thermal treatment 1 ~ 36 h under the more than recrystallization temperature condition of 20 ℃, naturally cool to room temperature, obtain transparent glass-ceramics;
(3) by AgNO
3and NaNO
3mix, or AgNO
3and KNO
3after mixing, obtain mixing salt, the transparent glass-ceramics then step (2) being obtained is imbedded in mixing salt, then at 250～450 ℃, carries out ion-exchange 10 min～72 h and obtains the devitrified glass after ion-exchange, AgNO in mixing salt
3molar percentage be 0.5 ~ 30%, NaNO
3or KNO
3molar percentage be 70 ~ 99.5%;
(4) devitrified glass after ion-exchange is heat-treated to 0.5 h～72 h under containing the condition of 30 ℃～150 ℃ below the glass transformation temperature of rare earth ion glass step (1) is prepared, obtain rear-earth-doped glass frequency inverted luminescent material.
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