CN1837419A - Ytterbium doped Y0.8LaCa4O(BO3)3 laser crystal, its preparation method and use - Google Patents

Ytterbium doped Y0.8LaCa4O(BO3)3 laser crystal, its preparation method and use Download PDF

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Publication number
CN1837419A
CN1837419A CN 200510063995 CN200510063995A CN1837419A CN 1837419 A CN1837419 A CN 1837419A CN 200510063995 CN200510063995 CN 200510063995 CN 200510063995 A CN200510063995 A CN 200510063995A CN 1837419 A CN1837419 A CN 1837419A
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crystal
laser
laser crystals
preparation
crystals
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CN1837419B (en
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王国富
韦波
林州斌
胡祖树
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

This invention provides a laser crystal adulterated with ytterbium boracic acid lanthanum oxygen calcium illinium lanthanum and its method for preparation and usage, which relates to a artificial crystal field, in particular to A laser crystal adulterated with ytterbium boracic acid lanthanum oxygen calcium illinium lanthanum and its method for preparation and usage. Using lifting and pulling method, at about 1500 degrees, with crystal rotary rate of 5-20 revolutions per minuten and pulling rate of 0.5-2 millimeter of hour, producing Yb3+:Ca3La2(BO3)4 crystal of top-quality and bigger size. The crystal is a new laser crystal, and can produce laser output of about 1 mum wavelength. The solid-state laser produed from the crystal can be used in many fields such as spectroscopy, biomedicine and military affairs.

Description

Blended ytterbium boric acid oxygen calcium yttrium lanthanum laser crystals and its production and use
Technical field
The present invention relates to artificial lens and growth field thereof, especially relate to a kind of laser crystal material as the operation material in the solid laser.
Background technology
Laser crystals is the operation material of solid statelaser, and it is meant with the crystal to be matrix, by discrete luminescence center absorptive pumping luminous energy and be translated into the luminescent material of laser output.Solid laser working substance is made up of substrate material and active ions, and its various physics and chemical property are mainly by the substrate material decision, and its spectral response curve and fluorescence lifetime etc. are then determined by the level structure of active ions.From nineteen sixty, succeeded in developing since the synthetic ruby pulsed laser, up to now, found hundreds of laser crystalss, but because of a variety of causes, the laser crystals that can really obtain practical application has only ten to plant.
At present, most widely used laser crystals is yttrium aluminum garnet (YAG) crystal of Nd ion doped, and it has various preferably physics and chemical property, and is easy to grow high optical quality, large-sized gem-quality crystal.But it is narrow that it exists spectral line of absorption, is unwell to the shortcoming of carrying out pumping with LD, and the LD pumping will be the developing direction of laser pumping source from now on.
All actively seek various physics, chemical property and mechanical property excellence both at home and abroad at present, and be easy to the high-quality laser crystal material that grows high optical quality, large size and be suitable for the LD pumping.Ytterbium ion is the simplest ion of level structure, and it absorbs bandwidth and effectively is coupled with InGaAs LD pumping source, is fit to very much the LD pumping.Than neodymium ion, ytterbium ion has many good qualities, and as not having excited state absorption and last conversion, has high fluorescence lifetime and light conversion efficiency or the like.Therefore, ytterbium ion becomes the choosing of the hot topic of laser crystals active ions in recent years.
Summary of the invention
Purpose of the present invention just is to develop a kind of new laser crystals Yb 3+: Y 0.8La 0.2Ca 4O (BO 3) 3, can directly use photoflash lamp and LD pumping, laser crystal material with higher conversion efficiency.
Yb 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Crystal belongs to oblique system, has Cm spacer structure.Wherein ytterbium ion is as dopant ion, replace the crystallographic site of yttrium and lanthanum ion, the doping content of ytterbium is between 1at.%~20at.%, and fluorescence lifetime (τ) is 1.5~3.0ms, its fluorescence lifetime is the function of ytterbium ion concentration, can mix the ytterbium ion of different concns according to different needs.Experimental result shows the laser of its exportable 1 μ m wavelength around, can be used as laser crystals.Yb 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Crystal is a kind of compound of congruent melting, adopts Czochralski grown to go out, and presses chemical equation: Ratio claim sample, mixing, compressing tablet, and Yb 2O 3Then pressing desired concn adds.Raw materials usedly be:
The medicine name Purity Producer
Yb 2O 3 99.999% Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences
Y 2O 3 99.999% Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences
La 2O 3 99.999% Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences
CaCO 3 99.99% Shanghai the May 4th chemical reagent factory
H 3BO 3 99.99% Shanghai chemical reagents corporation of Chinese Medicine group
Its main growth conditions is as follows: growth be in the iridium crucible, rare gas element is (as N 2, Ar etc.) carry out under the atmosphere, the parameter of crystal growth is about 1500 ℃ of growth temperatures, pulling speed is 0.5~2.0 millimeter/hour, 5~20 rev/mins of crystal rotating speeds have grown high-quality Yb 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Crystal.
With the Yb that grows 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Crystal has carried out the collection of diffraction data on four-circle diffractometer, structural analysis shows that it belongs to oblique system, spacer is Cm, and unit cell parameters is a=8.080 , b=16.022 , c=3.543 , β=101.22 °, V=449.9  3, density 3.39g/cm 3Adopting oil-immersion method to record its specific refractory power is 1.71.
With the Yb that grows 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Crystal carries out the analytical test of absorption spectrum, fluorescence spectrum and fluorescence lifetime etc., and the result shows: the ytterbium ion doping content is the Yb of 10.0at.% 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Crystalline master absorption peak is at 977nm, and its peak width at half height is 2nm, and the absorption jump cross section is 1.37 * 10 -20Cm 2, be suitable for adopting the InGaAs semiconductor laser to carry out pumping, help the absorption of laser crystals to pump light, improve pumping efficiency; The emission band that a non-constant width is arranged at the 900nm-1150nm place, wherein the emission transition cross section of emission peak 1033nm is 9.76 * 10 -21Cm 2, fluorescence lifetime is 2.69ms, the crystal that fluorescence lifetime is long can accumulate more particle at last energy level, has increased energy storage, helps the raising of device output rating and output energy.Therefore, Yb 3+u: Y 0.8La 0.2Ca 4O (BO 3) 3Crystal can obtain bigger output, is a kind of high conversion efficiency, low cost, high optical quality and actual application prospect is arranged and the laser crystals of use value.
Yb 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Crystal can grow superior in quality crystal easily with crystal pulling method, fast growth, the crystal quality is hard, has good heat-conducting, good optical characteristics is arranged, be easy to obtain laser output with flash lamp pumping and LD pumping, laser output wavelength is about 1 μ m, and this crystal can be used as a kind of laser crystals preferably.
Embodiment
Embodiment 1: the Czochralski grown doping content is 10.0at.%Yb 3+Yb 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Laser crystals.
Will be by the load weighted CaCO of proportion speed 3, Y 2O 3, La 2O 3, H 3BO 3, Yb 2O 3Mixed grinding is even, behind the compressing tablet, puts into φ 60 * 40mm 3Platinum alloy crucible in, in retort furnace in 800 ℃ of solid state reactions 12 hours; After the taking-up, grind compressing tablet again and be warming up to 1200 ℃ of reactions 24 hours again.Synthetic good above sample is put into the iridium crucible, adopt crystal pulling method, at N 2In the atmosphere, growth temperature is that 1505 ℃, crystal rotating speed are 12 rev/mins, and pulling rate is under 1 millimeter/hour the situation, to have grown and be of a size of 20 * 16 * 15mm 3High-quality Yb 3+Content is the Yb of 10.0at.% 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Crystal.
Embodiment 2: the Czochralski grown doping content is 15.0at.%Yb 3+Yb 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Laser crystals.
Will be by the load weighted CaCO of proportion speed 3, Y 2O 3, La 2O 3, H 3BO 3, Yb 2O 3Mixed grinding is even, behind the compressing tablet, puts into φ 60 * 40mm 3Platinum alloy crucible in, in retort furnace in 800 ℃ of solid state reactions 12 hours; After the taking-up, grind compressing tablet again and be warming up to 1200 ℃ of reactions 24 hours again.Synthetic good above sample is put into the iridium crucible, adopt crystal pulling method, in N2 atmosphere, growth temperature is that 1500 ℃, crystal rotating speed are 10 rev/mins, and pulling rate is under 1 millimeter/hour the situation, to have grown and be of a size of 25 * 22 * 15mm 3High-quality Yb 3+Content is the Yb of 15.0at.% 3+: Y 0.8La 0.2Ca 4O (BO 3) 3Crystal.

Claims (5)

1. blended ytterbium boric acid oxygen calcium yttrium lanthanum laser crystals, it is characterized in that: this crystalline molecular formula is Yb 3+: Y 0.8La 0.2Ca 4O (BO 3) 3, belonging to oblique system, spacer is Cm, unit cell parameters is a=8.080 , b=16.022 , c=3.543 , β=101.22 °, V=449.9 3, density 3.39g/cm 3, specific refractory power 1.71.
2. laser crystals as claimed in claim 1 is characterized in that: in this crystal, and Yb 3+Ion replaces Y in the crystal as dopant ion 3+And La 3+The ionic crystallographic site, its doping content is between 1at.-20at.%.
3. the preparation method of the laser crystals of a claim 1 is characterized in that: this crystal by adopting Czochralski grown, and with Y 2O 3, La 2O 3, CaCO 3, H 3BO 3And Yb 2O 3Be raw material, press chemical equation: Ratio claim sample, mixing, compressing tablet, and Yb 2O 3Then press desired concn and add, in the iraurite crucible, pulling growth goes out crystal under the inert gas atmosphere, and the parameter of crystal growth is about 1500 ℃ of growth temperatures, and pulling speed is 0.5~2.0 millimeter/hour, and the crystal rotating speed is 5~20 rev/mins.
4. the purposes of the laser crystals of a claim 1, it is characterized in that: this crystal is used for solid statelaser as working-laser material, uses photoflash lamp or laser diode (LD) as pumping source, excites the laser output that produces 1 μ m wavelength around.
5. the purposes of the laser crystals of a claim 1, it is characterized in that: the solid statelaser made from this crystal is used for spectroscopy, biomedicine, military field.
CN2005100639957A 2005-03-25 2005-03-25 Ytterbium doped calcium oxygen borate yttrium lanthanum laser crystal and preparation method and application thereof Expired - Fee Related CN1837419B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965730A (en) * 2011-09-01 2013-03-13 中国科学院福建物质结构研究所 Novel ytterbium-activating-gadolinium calcium borate ultrafast laser crystal
CN110528075A (en) * 2019-10-17 2019-12-03 中国工程物理研究院化工材料研究所 A kind of blended ytterbium boric acid calcium lanthanum yttrium mixed crystal laser crystal and its preparation method and application
CN110607558A (en) * 2019-10-17 2019-12-24 中国工程物理研究院化工材料研究所 Ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal and preparation method and application thereof
CN110863244A (en) * 2019-11-28 2020-03-06 中国工程物理研究院化工材料研究所 Ytterbium-doped strontium borate lanthanum yttrium mixed crystal laser crystal and preparation method and application thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965730A (en) * 2011-09-01 2013-03-13 中国科学院福建物质结构研究所 Novel ytterbium-activating-gadolinium calcium borate ultrafast laser crystal
CN110528075A (en) * 2019-10-17 2019-12-03 中国工程物理研究院化工材料研究所 A kind of blended ytterbium boric acid calcium lanthanum yttrium mixed crystal laser crystal and its preparation method and application
CN110607558A (en) * 2019-10-17 2019-12-24 中国工程物理研究院化工材料研究所 Ytterbium-doped calcium borate gadolinium yttrium mixed crystal laser crystal and preparation method and application thereof
CN110863244A (en) * 2019-11-28 2020-03-06 中国工程物理研究院化工材料研究所 Ytterbium-doped strontium borate lanthanum yttrium mixed crystal laser crystal and preparation method and application thereof

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