CN1332074C - Strontium-gadolinium borate ( Sr3Gd(BO3)3 ) laser crystal and its preparation method - Google Patents

Strontium-gadolinium borate ( Sr3Gd(BO3)3 ) laser crystal and its preparation method Download PDF

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CN1332074C
CN1332074C CNB031456820A CN03145682A CN1332074C CN 1332074 C CN1332074 C CN 1332074C CN B031456820 A CNB031456820 A CN B031456820A CN 03145682 A CN03145682 A CN 03145682A CN 1332074 C CN1332074 C CN 1332074C
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crystal
laser
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crystals
sr3gd
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CN1566413A (en
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王国富
潘建国
林州斌
胡祖树
张莉珍
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

The present invention relates to the field of an artificial crystal, particularly to laser crystals doped by neodymium and strontium gadolinium borate (Nd<3+>: Sr3Gd(BO3)3) and ytterbium and strontium gadolinium borate (Yb<3+>: Sr3Gd(BO3)3) and a preparation method thereof. The crystals belong to a trigonal system, space group is R3, and cell parameter satisfies the following formulae: a=12.521A, c=9.255A, V=1252A<3> and Z=6; density is 4.67 g/cm<3>, and refractivity is 1.73. An Nd<3+>: Sr3Gd(BO3)3 crystal and a Yb<3+>: Sr3Gd(BO3)3 crystal with high quality and large size are grown by adopting a crystal pulling method (Czochralski method), the growth condition comprises: growth temperature is about 1320 DEG C, the rotary speed of the crystal is from 10 to 15 revolutions per minute, and the pulling speed is from 0.5 to 1 mm/h; the crystals are suitable for pumping by adopting a laser diode (LD). A solid laser made from the crystals can be used for a plurality of fields of spectroscopy, biomedicine, military affairs, etc.

Description

Boracic acid gadolinium strontium laser crystals and preparation method thereof
Technical field
The present invention relates to artificial lens and field of crystal growth in the technical field of optoelectronic functional materials, especially relate to a kind of laser crystal material as the operation material in the solid laser.
Background technology
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, hundreds of laser crystalss have been found, but owing to reasons such as the heat of restriction, the crystal growth difficulty of gain, the spectrum property that is difficult to mix active ions, difference or difference and mechanical propertys, most laser crystal material all can not really drop in the practical application.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 not suitable for carrying out with LD the shortcoming of pumping, and the LD pumping will be the developing direction of laser pumping source from now on.
All actively seeking various physics, chemical property and mechanical property excellence both at home and abroad at present, and be easy to grow high optical quality, large-sized high-quality laser crystal material, and this crystal to be suitable for the LD pumping.Neodymium ion is used as active ions widely owing to have spectrum property preferably.The Yb ion does not exist conversion and excited state absorption because level structure is simple, and high light conversion efficiency and long fluorescence lifetime are arranged, and along with the development of superpower InGaAs laser two sharp pipes, the Yb ion also is used as active ions widely.The borate family crystal has better physical chemistry and mechanical property, and grows high-quality monocrystalline easily, becomes the choosing of the hot topic of laser host material.As crystal such as YCOB, GdCOB, YAB, Sr 3Gd (BO 3) 3Compound is two borate M 3Ln (BO 3) 3(M=Ca, Sr, Ba and Ln=La-Lu, Y) series compound is a kind of, is obtained powder at first by solid-phase synthesis.Also do not have at present growing crystal report.
Summary of the invention
Purpose of the present invention just is to develop a kind of new laser crystals, can directly use photoflash lamp and the laser crystal material LD pumping, that have higher conversion efficiency.
RE 3+: Sr 3Gd (BO 3) 3(wherein RE=Nd or Yb) crystal belongs to trigonal system, has The spacer structure.Wherein neodymium or ytterbium ion are as dopant ion, the crystallographic site that replaces gadolinium ion, the doping content of neodymium is between 0.05at%～10at%, when doping content is 3at%, fluorescence lifetime (τ) is 70 μ s, its fluorescence lifetime is the function of neodymium ion concentration, can mix the neodymium ion of different concns according to different needs.Experimental result shows the laser of its exportable 1060nm wavelength, can be used as working-laser material.The doping content of ytterbium is between 0.05at%-20at%, and when doping content was 15at%, fluorescence lifetime (τ) was 2.14ms, can produce the following ultra-short pulse laser of 100fs, also as tunable laser crystal.
Boracic acid gadolinium strontium is a kind of congruent compound, can adopt crystal pulling method (Czochralski method) to grow big monocrystalline.
Concrete chemical reaction is as follows: (1-x) Gd 2O 3+ xNd 2O 3+ 2Sr 3CO 3+ 6H 3BO 3→ 2Sr 3Gd (1-x)/2Nd X/2(BO 3) 3+ 2CO 2+ 9H 2O (1-x) Gd 2O 3+ xYb 2O 3+ 2Sr 3CO 3+ 6H 3BO 3→ 2Sr 3Gd (1-x)/2Yb X/2(BO 3) 3+ 2CO 2+ 9H 2O
Used material purity and producer are as follows:
The medicine name Purity Producer
Nd 2O 3 99.99％ Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences
Yb 2O 3 99.99％ Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences
SrCO 3 99.9％ Shanghai the May 4th chemical reagent factory
Gd 2O 3 99.99％ Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences
H 3BO 3 99.9％ Shanghai chemical reagents corporation of Chinese Medicine group
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 processing parameter of crystal growth is: growth temperature is about 1320 ℃, the crystal rotating speed is 10-15 rev/min, pull rate be the 0.5-1.0 millimeter/hour.Concrete process of growth is seen embodiment.
With the Nd that grows 3+: Sr 3Gd (BO 3) 3And yb 3+: Sr 3Gd (BO 3) 3Crystal has carried out the collection of diffraction data on four-circle diffractometer, structural analysis shows that it belongs to trigonal system, and spacer is
Figure C0314568200041
, unit cell parameters is a=12.521 , c=9.255 , V=1252  3, Z=6, density 4.67g/cm 3Adopting oil-immersion method to record its specific refractory power is 1.73.
With the Nd that grows 3+: Sr 3Gd (BO 3) 3Crystal carries out the analytical test of absorption spectrum, fluorescence spectrum and fluorescence lifetime etc., and the result shows: mix Nd concentration when 3at%, Nd 3+: Sr 3Gd (BO 3) 3Crystalline master absorption peak is at 807nm, and its peak width at half height is 16 nm, and the absorption jump cross section is 2.78 * 10 -20Cm 2, be very suitable for adopting the AsGaAl semiconductor laser to carry out pumping in the bigger peak width at half height in 807nm place, help the absorption of laser crystals to pump light, improve pumping efficiency.It is at the emission transition cross section σ at 1060nm place EmBe 1.61 * 10 -19Cm 2, peak width at half height (FWHM) is 23.3nm, fluorescence lifetime is 70 μ s,
With the Yb that grows 3+: Sr 3Gd (BO 3) 3Crystal carries out the analytical test of absorption spectrum, fluorescence spectrum and fluorescence lifetime etc., and the result shows: mix Yb concentration when 15at%, Yb 3+: Sr 3Gd (BO 3) 3Crystalline master absorption peak is at 976nm, and its peak width at half height is 7nm, and the absorption jump cross section is 6.57 * 10 -21Cm 2, be very suitable for adopting the InGaAl semiconductor laser to carry out pumping in the bigger peak width at half height in 976nm place, help the absorption of laser crystals to pump light, improve pumping efficiency.It is at the emission transition cross section σ at 1020nm place EmBe 2.3 * 10 -21Cm 2, peak width at half height (FWHM) is 83nm, fluorescence lifetime is 2.14ms.
Embodiment
Realize that preferred version of the present invention is as follows:
Embodiment 1, be 3.0at.%Nd with crystal pulling method (Czochralski method) grow doping concentration 3+Sr 3Gd (BO 3) 3Laser crystals.
Will be by the accurate load weighted Gd of stoichiometric ratio 2O 3, Nd 2O 3, Sr 3CO 3, H 3BO 3Mix, grind evenly, behind the compressing tablet, in retort furnace under 900 ℃ of conditions solid phase synthesis 24 hours, be warming up to 1000 ℃ of solid phase synthesis again 24 hours, the sample that solid phase synthesis is the good Φ 70 * 50mm that packs into 3Iridium Crucible and place lifting furnace, adopt crystal pulling method, at N 2In the atmosphere, growth temperature is about 1320 ℃, and the crystal rotating speed is 10 rev/mins, and pull rate is under 1.0 millimeters/hour the condition, to have grown and be of a size of Φ 30 * 35mm 3High-quality Nd 3+: Sr 3Gd (BO 3) 3Crystal.Measure through electronic probe that the Nd ionic concn is 1.336 * 10 in the crystal 20Cm -3
Embodiment 2, be 15.0at.%Yb with crystal pulling method (Czochralski method) grow doping concentration 3+Sr 3Gd (BO 3) 3Laser crystals.
Will be by the accurate load weighted Gd of stoichiometric ratio 2O 3, Yb 2O 3, Sr 3CO 3, H 3BO 3Mix, grind evenly, behind the compressing tablet, in retort furnace under 900 ℃ of conditions solid phase synthesis 24 hours, be warming up to 1000 ℃ of solid phase synthesis again 24 hours, the sample that solid phase synthesis is the good Φ 70 * 50mm that packs into 3Iridium Crucible and place lifting furnace, adopt crystal pulling method, at N 2In the atmosphere, growth temperature is about 1320 ℃, and the crystal rotating speed is 15 rev/mins, and pull rate is under 0.6 millimeter/hour the condition, to have grown and be of a size of Φ 25 * 30mm 3High-quality Yb 3+: Sr 3Gd (BO 3) 3Crystal.Measure through electronic probe that the Nd ionic concn is 6.208 * 10 in the crystal 20Cm -3

Claims (5)

1. boracic acid gadolinium strontium laser crystals, it is characterized in that: this crystalline molecular formula is RE 3+: Sr 3Gd (BO 3) 3, RE is Nd or Yb ion in the formula, belongs to trigonal system, spacer is , unit cell parameters is a=12.521 , c=9.255 , V=1252  3, Z=6, density 4.67g/cm 3, specific refractory power 1.73.
2. laser crystals as claimed in claim 1 is characterized in that: Nd 3+Ion replaces the case of gadolinium ion in the crystal as dopant ion, and its doping content is 0.05at-10at%.
3. laser crystals as claimed in claim 1 is characterized in that: yb 3+Ion replaces the case of gadolinium ion in the crystal as dopant ion, and its doping content is 0.05at-20at%.
4. the preparation method of the laser crystals of a claim 1 is characterized in that: this crystal by adopting Czochralski grown, growth conditions is: growth temperature is at 1320 ℃, and the crystal rotating speed is 10-15 rev/min, pull rate be the 0.5-1.0 millimeter/hour.
5. the purposes of the laser crystals of stating as claim 1 is characterized in that: with the solid statelaser that this crystal is made, use photoflash lamp or laser diode as pumping source, excite the laser output that produces the 1060nm wavelength, or produce femtosecond laser.
CNB031456820A 2003-07-10 2003-07-10 Strontium-gadolinium borate ( Sr3Gd(BO3)3 ) laser crystal and its preparation method Expired - Fee Related CN1332074C (en)

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CN102766905B (en) * 2011-05-04 2016-02-17 中国科学院福建物质结构研究所 Erbium ion activated 1.55 micron waveband gallate laser crystalss and preparation method thereof
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

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CN1250115A (en) * 1998-10-05 2000-04-12 中国科学院福建物质结构研究所 Self-frequency doubling laser crystal of Nd-doped low temperature phase lanthanum-scandium borate

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CN1250115A (en) * 1998-10-05 2000-04-12 中国科学院福建物质结构研究所 Self-frequency doubling laser crystal of Nd-doped low temperature phase lanthanum-scandium borate

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