CN101705518A - Bi-doped solonetz borate crystal and preparation method and application thereof - Google Patents

Bi-doped solonetz borate crystal and preparation method and application thereof Download PDF

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CN101705518A
CN101705518A CN200910151678A CN200910151678A CN101705518A CN 101705518 A CN101705518 A CN 101705518A CN 200910151678 A CN200910151678 A CN 200910151678A CN 200910151678 A CN200910151678 A CN 200910151678A CN 101705518 A CN101705518 A CN 101705518A
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solonetz
doped
crystal
borate crystal
borate
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CN101705518B (en
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苏良碧
徐军
李红军
周朋
喻军
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Shanghai de si Kai fluorine Photoelectric Technology Co.,Ltd.
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a Bi-doped solonetz borate crystal and a preparation method and application thereof, belonging to the field of optical crystal. In the Bi-doped solonetz borate crystal, the solonetz metal contains Ca, Sr and Ba, and the Bi ion doping density is 0.1-0.6at percent. The invention also further discloses preparation and application of the Bi-doped solonetz borate crystal. The Bi-doped solonetz borate crystal has very wide emission spectrum in a near-infrared range, and therefore, the crystal can be applied to wavelength tunable or ultrashort pulse lasers.

Description

Bi-doped solonetz borate crystal and its production and application
Technical field
The present invention relates to a kind of bi-doped solonetz borate crystal and its production and application, be mainly used in and produce wide wavelength tuning and ultra-short pulse laser output, belong to the optical crystal field.
Background technology
Pulse width be the laser of femtosecond magnitude with characteristics such as its ultrashort pulse that has, high-peak power and wide spectrum, have a wide range of applications in various fields such as ultrafast spectroscopy, microelectronics processing, light clock, metering, holography, heavy body optical communications.The femto-second laser based on titanium gem crystal that grow up the nineties in 20th century is can obtain short pulse at present, use maximum ultrafast laser devices, mainly by laboratory study and application.Because the 532nm pumping source volume of titanium jewel is big, electrical efficiency is low, cost an arm and a leg, limited its as commercial femto-second laser to miniaturization, direction develops cheaply.So the femto-second laser of miniature laser diode (LD) pump-coupling becomes the focus of Development of New Generation compact type, high-level efficiency, low-cost commercial femto-second laser.
Although mix Yb 3+Laserable material is being obtained certain achievement aspect the diode pumping generation ultrafast laser, but is subject to rare earth ion inherent narrow-band spectrum characteristic, and its SESAM mode-locked laser pulse width is generally magnitude of subnanosecond.The mode locking pulse that minority is mixed the Yb laser crystals can be less than 100fs, but average output power generally is lower than 100mW, also can't reach realistic scale.
Except that transition metal ion and rare earth ion, main group metal ion (as Bi, Pb, T1, Te etc.) can be classified as the 3rd Class Activation ion.Similar with transition metal ion, main group metal ionic valence electron does not have the shielding effect of out-shell electron, interact by force with crystal field, so the non-constant width of absorption, emmission spectrum of transition of electron formation.Nearest Japanese scholar Fujimoto has found to mix Bi ion glass first and has had broad-band illumination (FWHM＞200nm) and light amplification at near-infrared band 1000-1600nm, its emmission spectrum width has almost covered the overall optical communication band much larger than the similar glass (FWHM is about 40nm) of Er ion doping.Subsequently, the Qiu Jianrong of China professor research group infers tentatively that according to its relevant research work infraluminescence mechanism is the Bi ion of lower valency.2005, Russian scientist realized laser output, optical maser wavelength 1150-1300nm first in mixing Bi optical fiber.Obviously, the Bi ion mixes in the crystal with ordered structure will be more much higher than the luminous quantum efficiency of the glass of disordered structure, and the threshold power of laser generation is also much lower.
Summary of the invention
The purpose of this invention is to provide a kind of bi-doped solonetz borate crystal and its production and application.
The present invention's screening has suitable ingredients, is easy to the compound of growing single-crystal as Bi ionic doped substrate, by mixing the charge compensation ion altogether, optimize crystal growth technique, what acquisition had infrared 1.0～1.5 mu m waveband broad-band illumination characteristics mixes the Bi single crystal, can be applicable to produce the laser output that wavelength tuning range is wide and mode locking pulse is short.
According to existing bibliographical information, preparation is mixed Bi glass and is helped improving infraluminescence intensity under certain reducing atmosphere, and bismuth oxide raw material (Bi 2O 5Or Bi 2O 3) the following Bi ion that can resolve into lower valency of high temperature.Therefore, the deducibility of infraluminescence mechanism is the Bi ion of lower valency: Bi 2+Or Bi +Again in conjunction with following foundation:
(1) mixing the Bi glass Infrared fluorescence life-span is generally the ms magnitude;
(2) Bi 2+Ion and Ti atom isoelectronic, Pb with it +Ionic first excited state fluorescence lifetime is μ s magnitude;
(3) and and Bi +The isoelectronic Pb atom of ion first excited state fluorescence lifetime is the ms magnitude.
Thus, we infer that Bi ion infraluminescence center is Bi +Ion.
The present invention is based on following some screening host crystal:
(1) Bi +Ionic radius big (about 145pm), then the center positively charged ion of compound should be the suitable with it lower valency ion of ionic radius (+2 ,+1);
(2) do not contain valence state in the component of compound to be higher than+the center positively charged ion of divalent;
(3) compound grows into single crystal easily;
(4) single crystal has heat, mechanical integrated performance preferably, and is suitable to laser host.
Thus, the present invention adopts the alkaline earth metal borate crystal to make matrix, Ba in the alkaline-earth metal 2+The best, Sr 2+Take second place Ca 2+More take second place.
Bi ion doping concentration is in the bi-doped solonetz borate crystal that the present invention relates to: 0.1at%～6.0at%, and preferred doping content is: 0.1at%～5.0at%; Preferred doping content is 0.5at%～3.0at%.
Preferably, described bi-doped solonetz borate crystal is selected from Bi:BaB 2O 4Crystal, Bi:BaB 4O 7Crystal or Bi:SrB 4O 7Crystal.
The bi-doped solonetz borate crystal that the present invention relates to simultaneously can mix high valence state ion mixing the Bi ionic, mainly be valence stability, visible and near infrared region is inactive+3 ,+4 valency ions, specifically be meant Y 3+, La 3+, Zr 4+, Si 4+Plasma.Mix the ionic mixed ratio altogether and be the Bi ionic concn 0～5 times, better ratio is 0.1～4.5 times, and preferred proportion is 1～2 times.
The growing method of bi-doped solonetz borate crystal of the present invention adopts the melt method for growing technology to carry out crystal growth.During crystal growth in the burner hearth atmosphere adopt inertia or week reduction gas, particularly, can be nitrogen, argon gas or they respectively with H 2Mix the mixed gas that forms, wherein the H of mixed gas 2Ratio be 0.1at%～5at%.
Preferably, after described employing melt method for growing technology is carried out crystal growth and finished, also need to adopt the high energy hertzian wave that the bi-doped solonetz borate crystal that growth obtains is carried out irradiation.
Preferred, described high energy hertzian wave is gamma-rays or X ray; Wherein, described x-ray source is that wavelength 0.01nm～0.1nm, energy are the hard X ray of 10KeV～100KeV; Described gamma-rays is 60Co γ is as gamma-rays that irradiation source produced.
Preferred, in the described irradiation process, the irradiation dose scope is 1KGy～100KGy, and dose rate is 50Gy/h～500Gy/h.
Described crystal growth method by melt method is selected from: falling crucible method, crystal pulling method or kyropoulos.Other parameters of described melt method for growing technology can be determined according to the size and the kind of institute's growing crystal by those skilled in the art with reference to state of the art.
Bi-doped solonetz borate crystal middle or low price attitude Bi ionic content height according to technical scheme growth of the present invention, the infrared broad-band illumination of the laser diode-pumped generation of 980nm (as shown in Figure 1). simultaneously, preparation method of the present invention utilize gamma-rays and X ray with the process of matter interaction in can offer atom, the energy that molecule and lattice are very high, produce unbound electron simultaneously, make defective or these characteristics that change such as foreign ion valence state and coordination structure in the material, make it have the characteristic of near-infrared super-broadband emission by the irradiation bi-doped solonetz borate crystal, and this bi-doped solonetz borate crystal is at the exciting of using emission wavelength to be positioned at the laser diode of 700nm～1100nm or solid statelaser generation near-infrared super-broadband emission down, the centre wavelength of luminescent spectrum is positioned at 1.2 μ m, halfwidth can be used for preparing all solid state greater than the bi-doped solonetz borate crystal of 110nm. process irradiation, the tunable wave length of miniaturization or ultrashort pulse laser are with a wide range of applications near infrared wide bandwidth wavelength tuning and ultra-short pulse laser output field.
Description of drawings
The Bi of preparation: α-BaB among Fig. 1 embodiment 1 2O 4Crystal excites the emmission spectrum that produces down at emission wavelength for the 980nm laser diode.
The Bi:BaB of preparation among Fig. 2 embodiment 7 2O 4Crystalline near infrared emmission spectrum figure.
The Bi:BaB of preparation among Fig. 3 embodiment 7 2O 4Crystalline extinction curve figure.
Embodiment
The invention will be further described below by embodiment, but should not limit protection scope of the present invention with this.
Embodiment 1:3at%Bi: α-BaB 2O 4Crystal
(1) adopts Bi 2O 3, BaCO 3And HBO 3Making raw material, is 3: 97 batchings in Bi, Ba atomicity ratio, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 12 hours at 800 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into high-purity argon gas behind the Pa, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi: α-BaB thus 2O 4Crystal;
(3) after the cutting of crystal blank process, the polished finish, test its emmission spectrum.It is the laser diode of 980nm that pumping source adopts emission wavelength, and test room temperature emmission spectrum as shown in Figure 1 on the Triax550 fluorescence spectrophotometer.
Embodiment 2:4at%Bi, 4at%Si: α-BaB 2O 4Crystal
(1) adopts Bi 2O 3, BaCO 3, HBO 3, SiO 2Make raw material, by Bi: Si: Ba atomicity ratio is to prepare burden at 4: 4: 92, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 10 hours at 800 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into high pure nitrogen behind the Pa, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi, Si: α-BaB thus 2O 4Crystal.
Embodiment 3:1at%Bi, 1.5at%Y: α-BaB 2O 4Crystal
(1) adopts Bi 2O 3, BaCO 3, HBO 3, Y 2O 3Make raw material, by Bi: Y: Ba atomicity ratio is to prepare burden at 1: 1.5: 97.5, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 12 hours at 750 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into hydrogen volume behind the Pa than the hydrogen-argon-mixed body that is 3%, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi, Y: α-BaB thus 2O 4Crystal.
Embodiment 4:0.5at%Bi, 1.5at%Si:SrB 4O 7Crystal
(1) adopts Bi 2O 3, SrCO 3, HBO 3, SiO 2Make raw material, by Bi: Si: Sr atomicity ratio is to prepare burden at 0.5: 1.5: 98, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 8 hours at 750 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into high-purity argon gas behind the Pa, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi, Si:SrB thus 4O 7Crystal.
Embodiment 5:5at%Bi:SrB 4O 7Crystal
(1) adopts Bi 2O 3, SrCO 3, HBO 3Make raw material, by Bi: Sr atomicity ratio is to prepare burden at 5: 95, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 12 hours at 750 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into hydrogen volume behind the Pa than the hydrogen-argon-mixed body that is 1.5%, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi:SrB thus 4O 7Crystal.
Embodiment 6: the employing dose rate is 50Gy/h, total dose 1kGy 60The Co gamma-ray irradiation prepares 0.1at%Bi: α-BaB 2O 4Crystal;
(1) adopts Bi 2O 3, BaCO 3And HBO 3Making raw material, is 0.1: 99.9 batching in Bi, Ba atomicity ratio, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 12 hours at 800 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into high-purity argon gas behind the Pa, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi: α-BaB thus 2O 4Crystal;
(3) adopt 60Co gamma-ray irradiation Bi: α-BaB 2O 4Crystal, radiation dose are 1KGy, and dose rate is 50Gy/h.
Embodiment 7: the employing dose rate is 100Gy/h, total dose 10kGy 60The Co gamma-ray irradiation prepares 0.2at%Bi: α-BaB 2O 4Crystal;
(1) adopts Bi 2O 3, BaCO 3And HBO 3Making raw material, is 0.2: 99.8 batching in Bi, Ba atomicity ratio, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 12 hours at 750 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into high-purity argon gas behind the Pa, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi: α-BaB thus 2O 4Crystal;
(3) adopt 60Co gamma-ray irradiation Bi: α-BaB 2O 4Crystal, radiation dose are 10KGy, and dose rate is 100Gy/h.The shown colour-change of sample is by the colourless light green that becomes behind this kind dosage pre-irradiation;
(4) detected result: with Bi: α-BaB 2O 4Crystal-cut is in blocks, and adopting emission wavelength is the laser diode of 808nm and 980nm, test result as shown in Figure 2, the emission spectra peak wavelength is positioned at 1.2 μ m, halfwidth is 110nm; Adopt Tektronix TDS3020 digital oscilloscope record 1139nm fluorescence intensity extinction curve (as shown in Figure 3) in time, obtaining fluorescence lifetime numerical value by single order exponential attenuation equation model experimental data is 526 μ s.
Embodiment 8: the employing dose rate is 500Gy/h, total dose 10kGy 60The Co gamma-ray irradiation prepares 0.5%Bi:BaB 4O 7Crystal
(1) adopts Bi 2O 3, BaCO 3And HBO 3Making raw material, is 0.5: 99.5 batching in Bi, Ba atomicity ratio, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 12 hours at 750 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into high-purity argon gas behind the Pa, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi:BaB thus 4O 7Crystal;
(3) adopt 60Co gamma-ray irradiation Bi:BaB 4O 7The crystal radiation dose is 10KGy, dose rate be behind this kind of 500Gy/h. dosage pre-irradiation the shown colour-change of sample by the colourless light green that becomes.
Embodiment 9: the employing dose rate is 500Gy/h, total dose 100kGy 60The Co gamma-ray irradiation prepares 1.0at%Bi:BaB 4O 7Crystal
(1) adopts Bi 2O 3, BaCO 3And HBO 3Making raw material, is 1.0: 99.0 batchings in Bi, Ba atomicity ratio, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 12 hours at 750 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into high-purity argon gas behind the Pa, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi:BaB thus 4O 7Crystal;
(3) adopt 60Co gamma-ray irradiation Bi:BaB 4O 7Crystal, radiation dose are 100KGy, and dose rate is 500Gy/h.
Embodiment 10: adopt the hard X ray irradiation of wavelength 0.1nm, 10KeV to prepare 3.0at%Bi:SrB 4O 7Crystal
(1) adopts Bi 2O 3, BaCO 3And HBO 3Making raw material, is 3.0: 97.0 batchings in Bi, Ba atomicity ratio, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 12 hours at 750 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into high-purity argon gas behind the Pa, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi:BaB thus 4O 7Crystal;
(3) adopt hard X ray irradiation Bi:SrB 4O 7Crystal, X ray wavelength 0.1nm, energy 10KeV.
Embodiment 11: adopt the hard X ray irradiation of wavelength 0.01nm, 100KeV to prepare 6.0at%Bi:SrB 4O 7Crystal
(1) adopts Bi 2O 3, SrCO 3, HBO 3Make raw material, by Bi: Sr atomicity ratio is to prepare burden at 6: 94, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 12 hours at 750 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into hydrogen volume behind the Pa than the hydrogen-argon-mixed body that is 1.5%, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi:SrB thus 4O 7Crystal;
(3) adopt hard X ray irradiation Bi:SrB 4O 7Crystal, X ray wavelength 0.01nm, energy 100KeV.
Embodiment 12:5at%Bi, 0.5at%Zr:SrB 4O 7Crystal
(1) adopts Bi 2O 3, SrCO 3, HBO 3, ZrO 2Make raw material, by Bi: Zr: Sr atomicity ratio is to prepare burden at 5: 0.5: 94.5, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 8 hours at 750 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into high-purity argon gas behind the Pa, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi, Sr:SrB thus 4O 7Crystal.
Embodiment 13:1at%Bi, 4.5at%La: α-BaB 2O 4Crystal
(1) adopts Bi 2O 3, BaCO 3, HBO 3, La 2O 3Make raw material, by Bi: La: Ba atomicity ratio is to prepare burden at 1: 4.5: 94.5, and thorough mixing is the back briquetting evenly, carries out solid phase synthesis in 12 hours at 750 ℃ sintering temperatures;
(2) muffin after will synthesizing is put into Frequency Induction Heating and is lifted in the Iridium Crucible in the burner hearth, opens vacuum system behind the closed furnace, treats that burner hearth air pressure reaches 10 -2Charge into hydrogen volume behind the Pa than the hydrogen-argon-mixed body that is 3%, open heating system then, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth ending obtains Bi, Y: α-BaB thus 2O 4Crystal.

Claims (10)

1. bi-doped solonetz borate crystal, the alkaline-earth metal in the described bi-doped solonetz borate crystal is Ca or Sr or Ba, Bi ion doping concentration is 0.1at%～6.0at%.
2. bi-doped solonetz borate crystal as claimed in claim 1 is characterized in that, described Bi ion doping concentration is 0.1at%～5.0at%.
3. bi-doped solonetz borate crystal as claimed in claim 2 is characterized in that, described Bi ion doping concentration is 0.5at%～3.0at%.
4. as the described bi-doped solonetz borate crystal of arbitrary claim among the claim 1-3, it is characterized in that, mix the Bi ionic and mix Y simultaneously 3+Or La 3+Or Zr 4+Or Si 4+
5. the bi-doped solonetz borate crystal described in claim 4 is characterized in that, mixes Y 3+Or La 3+Or Zr 4+Or Si 4+Ratio be 0.1～4.5 times of Bi ionic concn.
6. as the growth method of bi-doped solonetz borate crystal as described in arbitrary claim among the claim 1-5, be to adopt melt method for growing, crystal growth atmosphere adopts inertia or week reduction gas.
7. the growth method of bi-doped solonetz borate crystal as claimed in claim 6 is characterized in that, after described employing melt method for growing crystal finishes, also needs to adopt the high energy hertzian wave that the bi-doped solonetz borate crystal that growth obtains is carried out irradiation.
8. the growth method of bi-doped solonetz borate crystal as claimed in claim 7 is characterized in that, described high energy hertzian wave is selected from X ray or gamma-rays, and in the described irradiation process, the irradiation dose scope is 1KGy～100KGy, and dose rate is 50Gy/h～500Gy/h.
9. the growth method of bi-doped solonetz borate crystal as claimed in claim 8 is characterized in that, described X ray is that wavelength is that 0.01nm～0.1nm, energy are the hard X ray of 10KeV～100KeV; Described gamma-rays is 60Co γ is as gamma-rays that irradiation source produced.
10. the described bi-doped solonetz borate crystal of arbitrary claim is applied to pulsed laser, long tunable pulsed laser device or ultrashort pulse laser among the claim 1-5.
CN 200910151678 2008-10-08 2009-07-16 Bi-doped solonetz borate crystal and preparation method and application thereof Active CN101705518B (en)

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CN108265330A (en) * 2018-01-22 2018-07-10 暨南大学 A kind of double-doped yttrium aluminate novel near-infrared laser crystal of bismuth potassium and preparation method thereof

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CN1331791C (en) * 2002-10-22 2007-08-15 中国科学院福建物质结构研究所 Neodymium doped borate glass with high luminous quantum efficiency and its preparing method
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CN108265330A (en) * 2018-01-22 2018-07-10 暨南大学 A kind of double-doped yttrium aluminate novel near-infrared laser crystal of bismuth potassium and preparation method thereof

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