CN102603194B - Rare earth doped microcrystalline glass of precipitated beta-NaGdF4 nanocrystalline and preparation method thereof - Google Patents
Rare earth doped microcrystalline glass of precipitated beta-NaGdF4 nanocrystalline and preparation method thereof Download PDFInfo
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- CN102603194B CN102603194B CN201110436331.6A CN201110436331A CN102603194B CN 102603194 B CN102603194 B CN 102603194B CN 201110436331 A CN201110436331 A CN 201110436331A CN 102603194 B CN102603194 B CN 102603194B
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Abstract
The invention discloses rare earth doped microcrystalline glass of precipitated beta-NaGdF4 nanocrystalline and a preparation method thereof. The rare earth doped microcrystalline glass of the precipitated beta-NaGdF4 nanocrystalline is prepared from the following components in the mole percentage by weight: 65-70% of SiO2, 5-10% of B2O3, 5-10% of Na2O, 5-10% of NaF, 5-10% of GdF3 and 0.5-5% of YbF3 and ReF3, wherein the Re is one or several of Er3+, Tm3+ and Ho3+. In the preparation method, the rare earth doped oxyfluoride glass is prepared with a high-temperature fusion method and is subjected to thermal treatment at certain temperature to obtain the microcrystalline glass of which the nanocrystalline size is from several or tens of nanometer orders of magnitude. The microcrystalline glass is transparent, has an excellent physical and chemical performance and can be used for solar cells, light amplification materials, luminescence display materials and the like.
Description
Technical field
The present invention relates to a kind of rare earth ion doped devitrified glass, particularly relate to one and separate out β-NaGdF
4nanocrystalline rear earth doping oxygen fluorine borosilicate microcrystalline glass and preparation method thereof.
Background technology
Devitrified glass is a kind of superior performance, widely used novel material.Since devitrified glass occurs, there is larger breakthrough in all many-sides such as performance, manufacturing process.Along with the development of devitrified glass research level, people also have higher requirement to the Performance and quality of devitrified glass.Transparent oxygen fluorine devitrified glass is with its superior chemical stability, physical strength and higher luminous efficiency, obtain many devitrified glass investigators' favor, thisly be embedded in by fluoride microcrystal the oxygen fluorine devitrified glass forming in oxide glass matrix and have two special optical properties to make it different from traditional stupalith: the one, between the small size (general approximately tens nanometers) of microcrystal grain and crystallite and vitreous state, the nearly power loss of having avoided scattering to cause of mating of specific refractory power, makes it have the transparency of height; The 2nd, rare earth ion solubleness is large, and the preferential richness of rare earth ion of doping is amassed in fluoride microcrystal, thereby can be in the environment of low phonon energy.Therefore, rear-earth-doped oxygen fluorine devitrified glass has had both the feature that low, the rare earth luminous efficiency of fluoride matrix phonon energy is high and matrix of oxide physical and chemical performance stable, workability is strong, be the rear-earth-doped substrate material that a class is good, have a good application prospect in fields such as solar cell, light amplification and luminescence displays.
The luminescent properties of rear earth doping oxygen-fluorine devitrified glass is directly related with fluoride nano crystal.NaYF
4and NaGdF
4relaxation is low, luminous efficiency high to have Deng basic metal rare earth fluorine that phonon energy is low, multi-phonon is radiationless.NaYF
4and NaGdF
4all there are two kinds of crystalline structure: hexagonal crystallographic texture and cubic crystal structure, the wherein NaYF of hexagonal crystallographic texture
4to change substrate material in well-known the best, and the Ce of hexagonal crystallographic texture
3+and Tb
3+mix altogether NaGdF
4it is the highest luminescent material of current quantum yield.So far there are no to the relevant six side's phase NaGdF that separate out
4the report of nano crystal transparent oxygen fluorine devitrified glass.
Summary of the invention
The object of the present invention is to provide one to separate out six side's phase β-NaGdF
4nanocrystalline rare earth ion doped devitrified glass and preparation method thereof.This devitrified glass not only has good chemical stability and mechanical property, and has good luminescent properties.
For achieving the above object, one of the present invention is separated out β-NaGdF
4nanocrystalline rare earth ion doped devitrified glass is by molar content, composed of the following components:
SiO
2：65-70％，
B
2O
3：5-10％，
Na
2O：5-10％，
NaF：5-10％，
GdF
3：5-10％，
YbF
3and ReF
3: 0.5-5%,
Wherein Re is Er
3+, Tm
3+, Ho
3+in any or appoint several.
Preferably, Re of the present invention is Er
3+and Tm
3+.
Preferably, Re of the present invention is Tm
3+and Ho
3+.
Preferably, Re of the present invention is Er
3+.
Preferably, Re of the present invention is Tm
3+.
Preferably, Re of the present invention is Ho
3+.
The preparation method of rare earth ion doped devitrified glass of the present invention comprises the following steps: (1) takes various raw materials and fully mixes, and described raw material, by molar content, is respectively
SiO
2：65-70％，
B
2O
3：5-10％
Na
2cO
3or Na
2o:5-10%,
NaF：5-10％，
GdF
3：5-10％，
YbF
3and ReF
3: 0.5-5%,
Wherein Re is Er
3+, Tm
3+, Ho
3+in any or appoint several;
(2) mixture step (1) being obtained melts and is incubated 0.5-2 hour and obtains glass melt at 1450-1550 ℃,
(3) glass melt is poured in mould and carried out anneal, obtain forerunner's glass;
(4) forerunner's glass is carried out differential thermal curve analysis and is obtained the first recrystallization temperature of forerunner's glass, and heat-treat 0.5-12 hour near described the first recrystallization temperature or its, after be down to room temperature, obtain the transparent β-NaGdF that separates out
4nanocrystalline rare earth ion doped devitrified glass.
The invention has the beneficial effects as follows:
The present invention, by adjusting oxygen fluorine glass ingredient and optimizing thermal treatment process, has realized β-NaGdF
4nanocrystallinely in glass, separate out, due to rare earth ion and Gd
3+ionic radius close, and valence state is identical, part replaces Gd
3+thereby position enters into the β-NaGdF separating out
4in nanometer lattice.Be compared to silicate glass (phonon energy 1100cm
-1), β-NaGdF
4there is lower phonon energy (360cm
-1), reduce the radiationless relaxation rate of multi-phonon of rare earth ion, thereby the Up-conversion Intensity of rare earth ion in devitrified glass obviously improved.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure before and after embodiment 1 sample thermal treatment, and curve 1 represents the XRD curve before thermal treatment, and curve 2 is illustrated in the XRD curve of 610 ℃ of thermal treatments after 2 hours, and separating out crystalline phase is β-NaGdF
4.
Embodiment
Below in conjunction with specific embodiment, invention is described in further detail.
Embodiment 1: table 1 has provided the molar content of the each component of rare earth ion doped devitrified glass of embodiment 1.
Table 1
| Raw material | SiO 2 | B 2O 3 | Na 2CO 3 | NaF | GdF 3 | ErF 3 | YbF 3 |
| Component (mol%) | 65 | 10 | 8 | 5 | 10 | 0.5 | 1.5 |
Concrete preparation process is as follows: according to the each component molar content in table 1, accurately take analytically pure SiO
2, B
2o
3, Na
2cO
3, NaF and GdF
3and the ErF of spectroscopically pure (99.99%)
3and YbF
3, after fully mixing, pour in crucible, in the electric furnace of 1450 ℃, be incubated 0.5 hour, the glass melt of melting is poured into rapidly on mould, after glass ware forming, transfer to rapidly in annealing furnace, lower the temperature with stove after 2 hours 400 ℃ of annealing.The glass making is carried out to differential thermal analysis, and the first crystallization peak temperature that records glass is 610 ℃, and the glass sample after annealing, 610 ℃ of thermal treatments 12 hours, is closed to annealing furnace and is naturally cooled to room temperature, obtains transparent devitrified glass.As shown in Figure 1, test and contrast PDF card through X-ray powder diffraction, crystalline phase is β-NaGdF
4.Devitrified glass is carried out to the test of transmission electron microscope photoelectron spectrum and show, rare earth ion Er
3+and Yb
3+at β-NaGdF
4content in nanocrystalline is respectively 4 times and 6 times of its content in glassy phase, shows rare earth ion Er
3+and Yb
3+enter into the β-NaGdF separating out
4in nanocrystalline.By fluorescence spectrophotometer, glass before and after thermal treatment is carried out to luminescent properties test, under 980nm laser pumping, can be observed bright green (524nm, 542nm) and red (665nm) up-conversion luminescence, with thermal treatment not before the Up-conversion Intensity of green glow (542nm) improved two orders of magnitude.
Embodiment 2: table 2 has provided the molar content of the each component of rare earth ion doped devitrified glass of embodiment 2.
Table 2
| Raw material | SiO 2 | B 2O 3 | Na 2CO 3 | NaF | GdF 3 | TmF 3 | YbF 3 |
| Component (mol%) | 70 | 9.5 | 5 | 10 | 5 | 0.2 | 0.3 |
Concrete preparation process is as follows: according to the each component molar content in table 2, accurately take analytically pure SiO
2, B
2o
3, Na
2cO
3, NaF and GdF
3and the TmF of spectroscopically pure (99.99%)
3and YbF
3, after fully mixing, pour in crucible, in the electric furnace of 1530 ℃, be incubated 2 hours, the glass metal of melting is poured into rapidly on mould, after glass ware forming, transfer to rapidly in annealing furnace, lower the temperature with stove after 2 hours 500 ℃ of annealing.The glass making is carried out to differential thermal analysis, and the first crystallization peak temperature that records glass is 650 ℃, and the glass sample after annealing, 650 ℃ of thermal treatments 0.5 hour, is obtained to transparent glass-ceramics.Test and contrast PDF card through X-ray powder diffraction, crystalline phase is β-NaGdF
4.Devitrified glass is carried out to the test of transmission electron microscope photoelectron spectrum and show, rare earth ion Tm
3+and Yb
3+at β-NaGdF
4content in nanocrystalline is 2 times and 3 times of its content in glassy phase, shows rare earth ion Tm
3+and Yb
3+enter into the β-NaGdF separating out
4in nanocrystalline.By fluorescence spectrophotometer, glass before and after thermal treatment is carried out to luminescent properties test, under 980nm laser pumping, can be observed bright blueness (475nm) up-conversion luminescence, improved 10 times with the Up-conversion Intensity of blue light before thermal treatment not.
Embodiment 3: table 3 has provided the molar content of the each component of rare earth ion doped devitrified glass of embodiment 3.
Table 3
| Raw material | SiO 2 | B 2O 3 | Na 2O | NaF | GdF 3 | HoF 3 | YbF 3 |
| Component (mol%) | 68 | 5 | 5 | 7 | 10 | 0.5 | 4.5 |
Concrete preparation process is as follows: according to the each component molar content in table 3, accurately take analytically pure SiO
2, B
2o
3, Na
2o, NaF and GdF
3and the HoF of spectroscopically pure (99.99%)
3and YbF
3, after fully mixing, pour in crucible, in the electric furnace of 1500 ℃, be incubated 1 hour, the glass metal of melting is poured into rapidly on mould, after glass ware forming, transfer to rapidly in annealing furnace, lower the temperature with stove after 2 hours 500 ℃ of annealing.The glass making is carried out to differential thermal analysis, and the first crystallization peak temperature that records glass is 630 ℃, and the glass sample after annealing, 630 ℃ of thermal treatments 5 hours, is obtained to transparent glass-ceramics.Test and contrast PDF card through X-ray powder diffraction, crystalline phase is β-NaGdF
4.Devitrified glass is carried out to the test of transmission electron microscope photoelectron spectrum and show, rare earth ion Ho
3+and Yb
3+at β-NaGdF
4content in nanocrystalline is 3 times and 10 times of its content in glassy phase, shows rare earth ion Ho
3+and Yb
3+enter into the β-NaGdF separating out
4in nanocrystalline.By fluorescence spectrophotometer, glass before and after thermal treatment is carried out to luminescent properties test, under 980nm laser pumping, can be observed (543nm) up-conversion luminescence of strong green and weak redness (643nm) up-conversion luminescence, improved two orders of magnitude with the Up-conversion Intensity of green glow before thermal treatment not.
Embodiment 4: table 4 has provided the molar content of the each component of rare earth ion doped devitrified glass of embodiment 4.
Table 4
| Raw material | SiO 2 | B 2O 3 | Na 2CO 3 | NaF | GdF 3 | ErF 3 | TmF 3 | YbF 3 |
| Component (mol%) | 68 | 7 | 9 | 8 | 7.2 | 0.1 | 0.2 | 0.5 |
Concrete preparation process is as follows: according to the each component molar content in table 4, accurately take analytically pure SiO
2, B
2o
3, Na
2cO
3, NaF and GdF
3and the ErF of spectroscopically pure (99.99%)
3, TmF
3and YbF
3, after fully mixing, pour in crucible, in the electric furnace of 1500 ℃, be incubated 1.5 hours, the glass metal of melting is poured into rapidly on the mould of preheating, after glass ware forming, transfer to rapidly in annealing furnace, lower the temperature with stove after 2 hours 450 ℃ of annealing.The glass making is carried out to differential thermal analysis, and the first crystallization peak temperature that records glass is 630 ℃, and the glass sample after annealing, 630 ℃ of thermal treatments 7 hours, is obtained to transparent glass-ceramics.Test and contrast PDF card through X-ray powder diffraction, crystalline phase is β-NaGdF
4.Devitrified glass is carried out to the test of transmission electron microscope photoelectron spectrum and show, rare earth ion Er
3+, Tm
3+and Yb
3+at β-NaGdF
4content in nanocrystalline is respectively 1.5 times, 2 times and 3 times of its content in glassy phase, shows that rare earth ion has entered into the β-NaGdF separating out
4in nanocrystalline.By fluorescence spectrophotometer, glass before and after thermal treatment is carried out to luminescent properties test, under 980nm laser pumping, can be observed bright white up-conversion luminescence, can be used as luminescence display material.
Embodiment 5: table 5 has provided the molar content of the each component of rare earth ion doped devitrified glass of embodiment 5.
Table 5
| Raw material | SiO 2 | B 2O 3 | Na 2CO 3 | NaF | GdF 3 | HoF 3 | TmF 3 | YbF 3 |
| Component (mol%) | 67 | 6 | 10 | 9 | 6.5 | 0.2 | 0.3 | 1 |
Concrete preparation process is as follows: according to the each component molar content in table 5, accurately take analytically pure SiO
2, B
2o
3, Na
2cO
3, NaF and GdF
3and the HoF of spectroscopically pure (99.99%)
3, TmF
3and YbF
3, after fully mixing, pour in crucible, in the electric furnace of 1500 ℃, be incubated 0.5 hour, the glass metal of melting is poured into rapidly on mould, after glass ware forming, transfer to rapidly in annealing furnace, lower the temperature with stove after 2 hours 450 ℃ of annealing.The glass making is carried out to differential thermal analysis, and the first crystallization peak temperature that records glass is 620 ℃, and the glass sample after annealing, 620 ℃ of thermal treatments 2 hours, is obtained to transparent glass-ceramics.Test and contrast PDF card through X-ray powder diffraction, crystalline phase is β-NaGdF
4.Devitrified glass is carried out to the test of transmission electron microscope photoelectron spectrum and show, rare earth ion Ho
3+, Tm
3+and Yb
3+at β-NaGdF
4content in nanocrystalline is respectively 1 times, 2 times and 4.5 times of its content in glassy phase, shows that rare earth ion has entered into the β-NaGdF separating out
4in nanocrystalline.By fluorescence spectrophotometer, glass before and after thermal treatment is carried out to luminescent properties test, under 980nm laser pumping, can be observed bright white up-conversion luminescence, can be used as luminescence display material.
Above-described embodiment is used for the present invention that explains, rather than limits the invention, and in the protection domain of spirit of the present invention and claim, any modification and change that the present invention is made, all fall into protection scope of the present invention.
Claims (7)
1. separate out β-NaGdF for one kind
4nanocrystalline rare earth ion doped devitrified glass, is characterized in that: by molar content, composed of the following components:
SiO
2：65–70%，
B
2O
3：5–10%，
Na
2O：5–10%，
NaF：5–10%，
GdF
3：5–10%，
YbF
3and ReF
3: 0. 5 – 5%,
Wherein Re is Er
3+, Tm
3+, Ho
3+in any or appoint several.
2. rare earth ion doped devitrified glass according to claim 1, is characterized in that: described Re is Er
3+and Tm
3+.
3. rare earth ion doped devitrified glass according to claim 1, is characterized in that: described Re is Tm
3+and Ho
3+.
4. rare earth ion doped devitrified glass according to claim 1, is characterized in that: described Re is Er
3+.
5. rare earth ion doped devitrified glass according to claim 1, is characterized in that: described Re is Tm
3+.
6. rare earth ion doped devitrified glass according to claim 1, is characterized in that: described Re is Ho
3+.
7. a preparation method for rare earth ion doped devitrified glass claimed in claim 1, is characterized in that comprising the following steps:
(1) take various raw materials and fully mix, described raw material, by molar content, is respectively
SiO
2：65–70%，
B
2O
3：5–10%
Na
2cO
3or Na
2o:5 – 10%,
NaF：5–10%，
GdF
3：5–10%，
YbF
3and ReF
3: 0. 5 – 5%,
Wherein Re is Er
3+, Tm
3+, Ho
3+in any or appoint several;
(2) mixture step (1) being obtained is at 1450 – 1550
ounder C, melt and be incubated 0.5 – and within 2 hours, obtain glass melt,
(3) glass melt is poured in mould and carried out anneal, obtain forerunner's glass;
(4) forerunner's glass is carried out differential thermal curve analysis and is obtained the first recrystallization temperature of forerunner's glass, and heat-treat 0.5 – 12 hours near described the first recrystallization temperature or its, after be down to room temperature, obtain the transparent β-NaGdF that separates out
4nanocrystalline rare earth ion doped devitrified glass.
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| CN103395997B (en) * | 2013-07-23 | 2015-12-02 | 南京邮电大学 | A kind of white light LEDs rare earth doping transparent glass-ceramic and preparation method thereof |
| CN103951253B (en) * | 2014-05-08 | 2016-02-10 | 宁波大学 | Rare earth ion doped LiGdCl 4devitrified glass and preparation method thereof |
| CN104445955A (en) * | 2014-12-05 | 2015-03-25 | 南京奥依菲光电科技有限公司 | Tunable transparent glass ceramic light-emitting fluorophor for LED and preparation method of tunable transparent glass ceramic light-emitting fluorophor |
| CN108863086A (en) * | 2018-06-26 | 2018-11-23 | 南京邮电大学 | A kind of embedded with precious metal and the devitrified glass of rare-earth phosphor nucleocapsid and preparation method thereof |
| CN109354417B (en) * | 2018-12-20 | 2021-06-29 | 中国计量大学 | NaTbF is separated out4Nanocrystalline germanosilicate microcrystalline glass and preparation method thereof |
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| CN115448603A (en) * | 2022-10-28 | 2022-12-09 | 昆明理工大学 | Divalent trivalent europium ion coexisting oxyfluoride aluminosilicate glass ceramic and preparation thereof |
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| CN101265029A (en) * | 2008-04-08 | 2008-09-17 | 中国计量学院 | Rear earth doping oxygen-fluorine borosilicate microcrystalline glass and preparation method thereof |
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