CN101705518B - 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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CN101705518B
CN101705518B CN 200910151678 CN200910151678A CN101705518B CN 101705518 B CN101705518 B CN 101705518B CN 200910151678 CN200910151678 CN 200910151678 CN 200910151678 A CN200910151678 A CN 200910151678A CN 101705518 B CN101705518 B CN 101705518B
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crystal
solonetz
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borate crystal
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CN101705518A (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 preparation method and application
Technical field
The present invention relates to a kind of bi-doped solonetz borate crystal and its preparation method and application, mainly for generation of 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 at present short pulse, use maximum ultrafast laser devices, mainly by laboratory study and application.Because the 532nm pumping source volume of titanium jewel is large, electrical efficiency is low, expensive, limited its as commercial femto-second laser to miniaturization, future development 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 the intrinsic narrow-band spectrum characteristic of rare earth ion, 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 transition metal ion and rare earth ion, main group metal ion (such as Bi, Pb, T1, Te etc.) can be classified as the 3rd Class Activation ion.Similar with transition metal ion, the valence electron of main group metal ion interacts by force with crystal field without the shielding effect of out-shell electron, so the non-constant width of absorption, emmission spectrum of transition of electron formation.Recently Japanese scholars Fujimoto has found first to mix the Bi ion glass and has had broad-band illumination (FWHM＞200nm) and light amplification at near-infrared band 1000-1600nm, its emmission spectrum width is much larger than the similar glass (FWHM is about 40nm) of Er ion doping, nearly cover whole optical communication wave band.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 first in mixing Bi optical fiber, optical maser wavelength 1150-1300nm.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 preparation method and application.
The present invention's screening has suitable ingredients, is easy to the compound of growing single-crystal as the doped substrate of Bi ion, by mixing altogether the charge compensation ion, 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 conducive to improve infraluminescence intensity under certain reducing atmosphere, and bismuth oxide raw material (Bi 2O 5Or Bi 2O 3) can resolve into the Bi ion of lower valency under the 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 with it, Pb +The first excited state fluorescence lifetime of ion 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 large (about 145pm), then the center positively charged ion of compound should be with it suitable lower valency ion (+2 ,+1) of ionic radius;
(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 preferably heat, mechanical integrated performance, 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 can mix highly charged ions when mixing the Bi ion, mainly be valence stability, visible and near infrared region is inactive+3 ,+4 valency ions, specifically refer to Y 3+, La 3+, Zr 4+, Si 4+Plasma.The mixed ratio of mixing altogether ion is 0～5 times of Bi ionic concn, and 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 the crystal growth.Atmosphere adopts inertia or week reduction gas in crystal when growth burner hearth, 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, described employing melt method for growing technology carry out crystal growth complete after, 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 60The gamma-rays that Co γ produces as irradiation source.
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 by those skilled in the art with reference to state of the art, be determined according to size and the kind of institute's growing crystal.
The content of attitude Bi ion is high at a middle or low price according to the bi-doped solonetz borate crystal of technical scheme of the present invention growth, 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 simultaneously unbound electron, 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 using emission wavelength to be positioned at generation near-infrared super-broadband emission under the exciting of the laser diode of 700nm～1100nm or solid statelaser, the centre wavelength of luminescent spectrum is positioned at 1.2 μ m, and halfwidth is greater than 110nm.Bi-doped solonetz borate crystal through irradiation can be used for preparing tunable wave length or ultrashort pulse laser all solid state, miniaturization, is 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 is the emmission spectrum that the 980nm laser diode excites lower generation at emission wavelength.
The Bi:BaB of preparation among Fig. 2 embodiment 7 2O 4The near infrared spectroscopy figure of crystal.
The Bi:BaB of preparation among Fig. 3 embodiment 7 2O 4The extinction curve figure of crystal.
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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 12 hours under 800 ℃ temperature;
(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 -2Be filled with high-purity argon gas behind the Pa, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi: α-BaB 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, at Triax550 fluorescence spectrophotometer test room temperature emmission spectrum as shown in Figure 1.
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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 10 hours under 800 ℃ temperature;
(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 -2Be filled with high pure nitrogen behind the Pa, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi, Si: α-BaB 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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 12 hours under 750 ℃ temperature;
(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 -2Be filled with hydrogen volume behind the Pa than the hydrogen-argon-mixed body that is 3%, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi, Y: α-BaB 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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 8 hours under 750 ℃ temperature;
(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 -2Be filled with high-purity argon gas behind the Pa, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi, Si:SrB 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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 12 hours under 750 ℃ temperature;
(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 -2Be filled with hydrogen volume behind the Pa than the hydrogen-argon-mixed body that is 1.5%, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi:SrB 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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 12 hours under 800 ℃ temperature;
(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 -2Be filled with high-purity argon gas behind the Pa, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi: α-BaB 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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 12 hours under 750 ℃ temperature;
(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 -2Be filled with high-purity argon gas behind the Pa, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi: α-BaB 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 peak wavelength of emmission spectrum 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 first-order exponential decay 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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 12 hours under 750 ℃ temperature;
(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 -2Be filled with high-purity argon gas behind the Pa, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi:BaB 4O 7Crystal;
(3) adopt 60Co gamma-ray irradiation Bi:BaB 4O 7The crystal radiation dose is 10KGy, and dose rate is 500Gy/h.The shown colour-change of sample is by the colourless light green that becomes behind this kind dosage pre-irradiation.
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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 12 hours under 750 ℃ temperature;
(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 -2Be filled with high-purity argon gas behind the Pa, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi:BaB 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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 12 hours under 750 ℃ temperature;
(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 -2Be filled with high-purity argon gas behind the Pa, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi:BaB 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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 12 hours under 750 ℃ temperature;
(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 -2Be filled with hydrogen volume behind the Pa than the hydrogen-argon-mixed body that is 1.5%, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi:SrB 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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 8 hours under 750 ℃ temperature;
(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 -2Be filled with high-purity argon gas behind the Pa, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi, Sr:SrB 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, fully mixes rear briquetting, and sintering carried out solid phase synthesis in 12 hours under 750 ℃ temperature;
(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 -2Be filled with hydrogen volume behind the Pa than the hydrogen-argon-mixed body that is 3%, then open heating system, the intensification melt raw material, through sowing, necking down, shouldering, isometrical, ending, behind the cooling supervisor, growth finishes, and obtains thus Bi, Y: α-BaB 2O 4Crystal.

Claims (8)

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%, it is characterized in that, mixes Y when mixing the Bi ion 3+Or La 3+Or Zr 4+Or Si 4+, mix Y 3+Or La 3+Or Zr 4+ or Si 4+Ratio be 0.1～4.5 times of Bi ionic concn.
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. such as the growth method of bi-doped solonetz borate crystal as described in arbitrary claim among the claim 1-3, be to adopt melt method for growing, described melting method is selected from: falling crucible method, crystal pulling method or kyropoulos, the crystal growth atmosphere adopts inertia or week reduction gas.
5. the growth method of bi-doped solonetz borate crystal as claimed in claim 4 is characterized in that, after described employing melt method for crystal growth is complete, also needs to adopt the high energy hertzian wave that the bi-doped solonetz borate crystal that growth obtains is carried out irradiation.
6. the growth method of bi-doped solonetz borate crystal as claimed in claim 5 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.
7. the growth method of bi-doped solonetz borate crystal as claimed in claim 6 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 60The gamma-rays that Co γ produces as irradiation source.
8. the application of the described bi-doped solonetz borate crystal of arbitrary claim in pulsed laser, Wavelength tunable laser or ultrashort pulse laser among the claim 1-3.
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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CNA2008102009109A CN101386416A (en) 2008-10-08 2008-10-08 Bi-dopping alkali earth borate crystal and preparation method and application thereof
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US4234821A (en) * 1977-09-14 1980-11-18 Sharp Kabushiki Kaisha Flat panel television receiver implemented with a thin film EL panel
CN1211273A (en) * 1996-01-17 1999-03-17 罗狄亚化学公司 Rare earth borate and its precursor, preparation processes and use of borate as lumcinophore
CN1328526A (en) * 1998-09-03 2001-12-26 罗狄亚化学公司 Lanthanum, lutetium, yttrium or gadolinium borate comprising two doping agents and its precursor use in plasma or x-ray systems
CN1491910A (en) * 2002-10-22 2004-04-28 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
CN1645232A (en) * 2005-01-26 2005-07-27 中国科学院上海光学精密机械研究所 Bismuth ion doped crystal for tunable laser and wide-band amplifier

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4234821A (en) * 1977-09-14 1980-11-18 Sharp Kabushiki Kaisha Flat panel television receiver implemented with a thin film EL panel
CN1211273A (en) * 1996-01-17 1999-03-17 罗狄亚化学公司 Rare earth borate and its precursor, preparation processes and use of borate as lumcinophore
CN1328526A (en) * 1998-09-03 2001-12-26 罗狄亚化学公司 Lanthanum, lutetium, yttrium or gadolinium borate comprising two doping agents and its precursor use in plasma or x-ray systems
CN1491910A (en) * 2002-10-22 2004-04-28 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
CN1645232A (en) * 2005-01-26 2005-07-27 中国科学院上海光学精密机械研究所 Bismuth ion doped crystal for tunable laser and wide-band amplifier

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