CN103526294A - Crystalline material with intermediate infrared broadband luminescence property and preparation method thereof - Google Patents

Crystalline material with intermediate infrared broadband luminescence property and preparation method thereof Download PDF

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CN103526294A
CN103526294A CN201310485662.8A CN201310485662A CN103526294A CN 103526294 A CN103526294 A CN 103526294A CN 201310485662 A CN201310485662 A CN 201310485662A CN 103526294 A CN103526294 A CN 103526294A
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crystalline material
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唐慧丽
蒋先涛
苏良碧
徐军
吴锋
汪传勇
姜大朋
王静雅
钱小波
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention discloses a crystalline material with an intermediate infrared broadband luminescence property and a preparation method of the crystalline material. According to the crystalline material, Bi12GeO20 crystal is doped with a metal ionic material without luminescence property within wave band of 2-4mu m. The preparation method comprises the steps of (a) weighing Bi2O3 powder and GeO2 powder according to stoichiometric ratio of Bi12GeO20, then adding the powder into doped powder, and mixing uniformly; (b) preparing the mixed powder obtained in step (a) into a green body, sintering for 5-20 hours at 500-800 DEG C, then grinding, and obtaining doped Bi12GeO20 powder; and (c) preparing the Bi12GeO20 powder obtained in step (b) into the crystalline material with the intermediate infrared broadband luminescence property. The absorption edge of the crystalline material prepared by the method is 300nm, in 300-1100nm, the crystalline material has no obvious absorption peak, the fluorescence range of the crystalline material is 1800-3020nm, and the coverage wave band exceeds 1000nm, so that the crystalline material can be widely used in fields such as communication, medical treatment and military.

Description

A kind of have in the crystalline material and preparation method thereof of infrared broad-band illumination performance
Technical field
The present invention relates to a kind of have in the crystalline material and preparation method thereof of infrared broad-band illumination performance, belong to technical field of inorganic material.
Background technology
In broadband, infraluminescence is because it can be applied to laser (laser remote sensing, lidar, can coordinate laser, ultrafast laser), medical science (arthroscopy, urinary system treatment, dentistry and ophtalmic treatments), fields such as military (infrared acquisition, tracking, target acquistion, guidances), thereby enjoy domestic and international researchist's attention.At present research is many comprises semiconductor diode and QCL (majority is worked at low temperatures), and rare earth element and transition element doped material, as Tm 3+, Ho 3+, Er 3+, Dy 3+, Cr 2+, Co 2+deng.
From 1999, Japanese scientist Murata and Fujimoto found to have the near-infrared luminous of broadband containing the silica glass of Bi, and proposed it and there is tempting application prospect at optical-fibre communications field, numerous scientific research personnel has put into energy containing the outer luminescent properties near red broadband of the material of main group ion Bi element and has studied, and has but ignored wherein infraluminescence performance study.2009, first Hughes obtained mixing Bi chalcogenide glass in the fluorescent effect of 2000nm and 2600nm under 5K condition.2012 Nian， China researchist Cao are containing Bi 5(AlCl 4) 3material in observed the weak fluorescent effect of 1000-4000nm, and think that luminescence center is Bi 5 3+.Subsequently, Alexey is at AlCl 3/ ZnCl 2/ BiCl 3in glass system, under 77K condition, also observed the broadband fluorescent effect of 1300～2500nm, he also thinks that luminescence center is Bi 5 3+.Yet forefathers' material system also comes with some shortcomings, for example above phenomenon is observed mostly at low temperatures, contains Bi 5(AlCl 4) 3although material be infrared luminous in just having at ambient temperature, due to the preparation temperature very low (being less than 350 ℃) of its material, material is unstable, easily decomposes, the practicality of material need perfect.Comparatively speaking, Bi 12geO 20(claiming again yellow BGO) crystal technique is ripe, can prepare high quality large-size crystals, and physical and chemical performance is stable, is beneficial to processing, also can be drawn into as required optical fiber, can have good compatibility with other optical system, and shooting conditions is simple; The LD pumping of 300～1100nm that we adopt, can be good at utilizing now full-fledged diode laser as pumping source, thereby obtains compact type, high-level efficiency, low-cost commercial lasers device.
Bi 12geO 20crystal is found in the end of the sixties in last century, belongs to isometric system, point group 23, and color is pale yellow, and clear area is 0.45～7.5 μ m, 930 ℃ of fusing points, Chang Zuowei piezoelectricity and Electrooptic crystal material.In addition, this crystal also has a series of other excellent performances, as photorefractive effect, birefringence effect, rotation effect and good ultrasonic performance etc., is the multi-functional crystalline material of a high-quality.Because it has good physical and chemical performance, scientific research personnel, also once using it as laser host crystalline material, has studied the luminescent properties that mixes therein rare earth ion, has obtained a lot of good results.Yet, for pure Bi 12geO 20crystal and mix not the ion as luminescence center, and the research that obtains the middle infraluminescence of 2～3 μ m but rarely has report.
Summary of the invention
For the problems referred to above and the defect of prior art existence, the object of this invention is to provide a kind of Bi of the non-light emitting ionic that adulterated 12geO 20the preparation method of crystal is Bi 12geO 20the preparation of crystal provides new approach, to research Bi 12geO 20the luminescence mechanism of crystal provides new material.
For achieving the above object, the technical solution used in the present invention is as follows:
A crystalline material for infrared broad-band illumination performance in having is at Bi 12geO 20in crystal, adulterated and do not there is the crystalline material of the metal ion of luminescent properties in 2～4 mu m wavebands.
As a kind of preferred version, described metal ion is selected from Al 3+, Mg 2+, Ca 2+and Mo 6+in a kind of.
Of the present invention have in the preparation method of crystalline material of infrared broad-band illumination performance, comprise the steps:
A) press Bi 12geO 20stoichiometric ratio take Bi 2o 3powder and GeO 2after powder, add adulterated powder, mix;
B) mixed powder step being obtained in a) is made base substrate, and at 500～800 ℃, sintering ground after 5～20 hours, obtained the Bi of doping 12geO 20powder;
C) by step b) in the Bi that obtains 12geO 20powder is prepared into middle infraluminescence crystalline material.
As a kind of preferred version, the dosage of described adulterated powder is GeO 20.1～10% of the mole number of powder.
As further preferred version, described adulterated powder is selected from Al 2o 3, MgO, CaO and MoO 3in a kind of.
As a kind of preferred version, step c) in by Bi 12geO 20the method that powder is prepared into middle infraluminescence crystalline material is selected from a kind of in crystal pulling method, falling crucible method and temperature gradient method.
As further preferred version, the process regulation of described crystal pulling method is: crucible material is selected precious metal simple substance, system blanketing with inert gas, and pull rate is 1～4 milli m/h, rotating speed is 18～28 revs/min.
As further preferred version, the process regulation of described falling crucible method is: crucible material is selected precious metal simple substance or molybdenum simple substance, material temperature is 950～1050 ℃, crystal growth district thermograde is 20～40 ℃/centimetre, and during crystal growth, dropping speed of the crucible is 1～4 milli m/h.
As further preferred version, the process regulation of described temperature gradient method is: crucible material is selected precious metal simple substance, system is oxygen free condition, material temperature is 950～1050 ℃, the thermograde of crystal growth district is 20～40 ℃/centimetre, and during crystal growth, temperature lowering speed is 1～5 ℃/h.
As preferred version further, described precious metal is platinum or iridium.
Crystalline material prepared by the present invention, ABSORPTION EDGE is positioned at 300nm, in 300～1100nm scope, there is no obvious absorption peak, and fluorescence scope is 1800～3020nm, covers wave band and surpasses 1000nm, can be widely used in communication, medical treatment and the field such as military.
Accompanying drawing explanation
Fig. 1 is the ultraviolet spectrogram of the prepared crystal of the embodiment of the present invention 1;
Fig. 2 is the fluorescence spectrum figure of the prepared crystal of the embodiment of the present invention 1.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only for the present invention is described but not limit the scope of the invention.
Embodiment 1: Bridgman-Stockbarge method for growing 4%Mo:Bi 12geO 20crystal
One, according to Bi 2o 3and GeO 2mol ratio be that 6:1 takes Bi 2o 3powder and GeO 2powder, then add GeO 2the MoO of powder mole number 4% 3powder, after ground and mixed 10h, is pressed into pie, in air at 750 ℃ sintering 10h;
Two, the crystal raw material sintering is pulverized to grinding and proceed in platinum crucible, put into the crucible decline stove growing crystal that globars is made heating element, it is 1000 ℃ that material temperature is set, and dropping speed of the crucible is 2mm/h;
Three, the crystal of having grown is cut perpendicular to the direction of growth, sample size is 2 * 10 * 10mm, polishing; Adopt Jasco V-570UV/VIS/NIR spectrophotometer to test the room temperature absorption spectrum of sample, as shown in Figure 1, the ABSORPTION EDGE of sample is positioned at 300nm to test result; Utilizing FLSP920(Edinburgh instruments) time resolution fluorescence spectral instrument tested its Emission at Room Temperature spectrum, pumping source adopts emission wavelength to be positioned at laser diode or the solid statelaser of 300～1000nm wavelength region, as shown in Figure 2, fluorescence scope is 1800～3020nm to fluorescence pattern.
Embodiment 2: the pure Bi of Czochralski grown 12geO 20crystal
One, according to Bi 2o 3and GeO 2mol ratio be that 6:1 takes Bi 2o 3powder and GeO 2powder, then add GeO 2the Al of powder mole number 1% 2o 3powder, after ground and mixed 10h, is pressed into pie, in air at 800 ℃ sintering 10h;
Two, the crystal raw material pulverizing grinding sintering is proceeded to and is of a size of
Figure BDA0000396686690000031
iridium Crucible in, under the protection of high-purity argon gas, control pull rate is 3mm/h, rotating speed is 20r/min.
Embodiment 3: Bridgman-Stockbarge method for growing 2%Al:Bi 12geO 20crystal
One, according to Bi 2o 3and GeO 2mol ratio be that 6:1 takes Bi 2o 3powder and GeO 2powder, then add GeO 2the Al of powder mole number 1% 2o 3powder, after ground and mixed 10h, is pressed into pie, in air at 750 ℃ sintering 10h;
Two, the raw material pulverizing sintering is ground and proceeded in platinum crucible, put into the crucible decline stove growing crystal that globars is made heating element, it is 1000 ℃ that material temperature is set, and dropping speed of the crucible is 2mm/h.
Embodiment 4: Czochralski grown 1%Ca:Bi 12geO 20crystal
One, according to Bi 2o 3and GeO 2mol ratio be that 6:1 takes Bi 2o 3powder and GeO 2powder, then add GeO 2the CaO powder of powder mole number 1%, after ground and mixed 10h, is pressed into pie, in air at 750 ℃ sintering 10h;
Two, the raw material pulverizing sintering is ground and proceeded to be of a size of
Figure BDA0000396686690000043
iridium Crucible in, under the protection of high-purity argon gas, control pull rate is 3mm/h, rotating speed is 20r/min.
Embodiment 5: Czochralski grown 1%Mg:Bi 12geO 20crystal
One, according to Bi 2o 3and GeO 2mol ratio be that 6:1 takes Bi 2o 3powder and GeO 2powder, then add GeO 2the MgO powder of powder mole number 1%, after ground and mixed 10h, is pressed into pie, in high-purity argon gas at 750 ℃ sintering 10h;
Two, the crystal raw material pulverizing grinding sintering is proceeded to and is of a size of
Figure BDA0000396686690000044
iridium Crucible in, under the protection of high-purity argon gas, control pull rate is 3mm/h, rotating speed is 20r/min.
Embodiment 6: Growth by Temperature Gradient Technique 2%Al:Bi 12geO 20crystal
One, according to Bi 2o 3and GeO 2mol ratio be that 6:1 takes Bi 2o 3powder and GeO 2powder, then add GeO 2the Al of powder mole number 1% 2o 3powder, after ground and mixed 10h, is pressed into pie, in high-purity argon gas at 750 ℃ sintering 10h;
Two, the raw material pulverizing sintering is ground and proceed in platinum crucible, be filled with sealed crucible after high-purity argon gas, put into the temperature gradient furnace growing crystal that adopts high purity graphite to make heating element, after vacuumizing in burner hearth, be filled with high-purity argon gas, it is 1000 ℃ that material temperature is set, cooling growth after insulation 3h, temperature lowering speed is 2 ℃/h.
Uv-absorbing intensity and fluorescent emission intensity that in embodiment 2～6, the crystal of preparation detects by the method in embodiment 1 respectively, result is consistent with the result of embodiment 1.
Finally be necessary described herein: above embodiment is only for being described in more detail technical scheme of the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.

Claims (10)

1. a crystalline material for infrared broad-band illumination performance in having, is characterized in that: be at Bi 12geO 20in crystal, adulterated and do not there is the metal ion of luminescent properties in 2～4 mu m wavebands.
2. crystalline material as claimed in claim 1, is characterized in that: described metal ion is selected from Al 3+, Mg 2+, Ca 2+and Mo 6+in a kind of.
3. a preparation method for crystalline material as claimed in claim 1, is characterized in that, comprises the steps:
A) press Bi 12geO 20stoichiometric ratio take Bi 2o 3powder and GeO 2after powder, add adulterated powder, mix;
B) mixed powder step being obtained in a) is made base substrate, and at 500～800 ℃, sintering ground after 5～20 hours, obtained the Bi of doping 12geO 20powder;
C) by step b) in the Bi that obtains 12geO 20infrared broad-band illumination crystalline material during powder is prepared into.
4. preparation method as claimed in claim 3, is characterized in that: the dosage of described adulterated powder is GeO 20.1～10% of the mole number of powder.
5. preparation method as claimed in claim 3, is characterized in that: described adulterated powder is selected from Al 2o 3, MgO, CaO and MoO 3in a kind of.
6. preparation method as claimed in claim 3, is characterized in that: step c) by Bi 12geO 20during powder is prepared into, the method for infrared broad-band illumination crystalline material adopts a kind of in crystal pulling method, falling crucible method and temperature gradient method.
7. preparation method as claimed in claim 6, is characterized in that, the process regulation of described crystal pulling method is: crucible material is selected precious metal simple substance, system blanketing with inert gas, and pull rate is 1～4 milli m/h, rotating speed is 18～28 revs/min.
8. preparation method as claimed in claim 6, it is characterized in that, the process regulation of described falling crucible method is: crucible material is selected precious metal simple substance or molybdenum simple substance, material temperature is 950～1050 ℃, crystal growth district thermograde is 20～40 ℃/centimetre, and during crystal growth, dropping speed of the crucible is 1～4 milli m/h.
9. preparation method as claimed in claim 6, it is characterized in that, the process regulation of described temperature gradient method is: crucible material is selected precious metal simple substance, system is oxygen free condition, material temperature is 950～1050 ℃, the thermograde of crystal growth district is 20～40 ℃/centimetre, and during crystal growth, temperature lowering speed is 1～5 ℃/h.
10. the preparation method as described in claim 7 or 8 or 9, is characterized in that: described precious metal is platinum or iridium.
CN201310485662.8A 2013-10-16 2013-10-16 Crystalline material with intermediate infrared broadband luminescence property and preparation method thereof Pending CN103526294A (en)

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CN112723751A (en) * 2020-10-23 2021-04-30 南京同溧晶体材料研究院有限公司 Rare earth doped bismuth germanate single crystal optical fiber and cladding method

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Publication number Priority date Publication date Assignee Title
CN112723751A (en) * 2020-10-23 2021-04-30 南京同溧晶体材料研究院有限公司 Rare earth doped bismuth germanate single crystal optical fiber and cladding method
CN112723751B (en) * 2020-10-23 2022-03-11 南京同溧晶体材料研究院有限公司 Rare earth doped bismuth germanate single crystal optical fiber and cladding method

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