CN101676446B - Neodymium-doped lanthanum barium lithium molybdate laser crystal and preparation method and application thereof - Google Patents

Neodymium-doped lanthanum barium lithium molybdate laser crystal and preparation method and application thereof Download PDF

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CN101676446B
CN101676446B CN 200810071783 CN200810071783A CN101676446B CN 101676446 B CN101676446 B CN 101676446B CN 200810071783 CN200810071783 CN 200810071783 CN 200810071783 A CN200810071783 A CN 200810071783A CN 101676446 B CN101676446 B CN 101676446B
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crystal
laser
neodymium
lithium molybdate
doped lanthanum
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CN101676446A (en
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王国富
宋明君
张莉珍
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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

The invention relates to a neodymium-doped lanthanum barium lithium molybdate laser crystal and a preparation method and application thereof. The high-quality Nd<3+>:Li3Ba2La3(MoO4)8 crystal with large size is grown by using 60-80at% Li2MoO4 as a fluxing agent under the conditions that the cooling rate is 0.5-2 DEG C/day and the rotating speed is 5-30r/min. The crystal belongs to the monoclinic system and has C2/c space group structure. The crystal is a novel laser crystal and can generate and output lasers with wavelength being about 1.06mu m. The solid lasers prepared by the crystal can be applied to such fields as spectroscopy, biomedicine, military affairs and the like.

Description

Neodymium-doped lanthanum barium lithium molybdate laser crystal and its production and use
Technical field
Neodymium-doped lanthanum barium lithium molybdate laser crystal and its production and use, it relates to artificial lens and field of crystal growth in the technical field of optoelectronic functional materials, especially relates 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 refers to 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 determined by substrate material that mainly 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 physics and chemical property preferably, 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.Neodymium-doped lanthanum barium lithium molybdate laser crystal and its production and use, the purpose of its invention just are to develop a kind of new laser crystals, can directly use photoflash lamp and LD pumping, the laser crystal material with higher conversion efficiency.
Summary of the invention
Purpose of the present invention just is to develop a kind of new laser crystals Nd 3+: Li 3Ba 2La 3(MoO 4) 8, can directly use photoflash lamp and LD pumping, the laser crystal material with higher conversion efficiency.Nd 3+: Li 3Ba 2La 3(MoO 4) 8Crystal belongs to oblique system, has C2/c spacer structure.Wherein neodymium ion is as dopant ion, replace the crystallographic site of lanthanum ion, the doping content of neodymium is between 0.5at.% ~ 15at.%, and fluorescence lifetime (τ) is 0.1 ~ 0.2ms, 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 1.06 μ m wavelength around, can be used as laser crystals.
Neodymium-doped lanthanum barium lithium molybdate laser crystal and preparation method thereof: we have found growth of Nd through experiment 3+: Li 3Ba 2La 3(MoO 4) 8The comparatively ideal fusing assistant of crystal: Li 2MoO 4, and best growth conditions, and grown high-quality crystal Nd 3+: Li 3Ba 2La 3(MoO 4) 8(seeing embodiment 1).
Concrete chemical equation is as follows:
3Li 2CO 3+4BaCO 3+3La 2O 3+16MoO 3=2Li 3Ba 2La 3(MoO 4) 8+7CO 2
Li 2CO 3+MoO 3=Li 2MoO 4+CO 2
Used material purity and producer are as follows:
The medicine name Purity Producer
Nd 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
Li 2CO 3 99.9% Reagent company limited of traditional Chinese medicines group
BaCO 3 99.99% Reagent company limited of traditional Chinese medicines group
MoO 3 99.99% Shanghai chemical reagents corporation of Chinese Medicine group
Case of flux methods growth neodymium-doped lanthanum barium lithium molybdate laser crystal, its main growth conditions is as follows: used fusing assistant is Li 2MoO 4, the total concentration of fusing assistant is controlled between 60 ~ 80at%, and growth temperature is between 750 ~ 900 ℃, and rate of temperature fall is 0.5 ~ 2 ℃/day, and rotating speed is 5 ~ 30rpm.
With the Nd that grows 3+: Li 3Ba 2La 3(MoO 4) 8Crystal has carried out the collection of diffraction data at four-circle diffractometer, and structural analysis shows that it belongs to oblique system, has C2/c spacer structure, and unit cell parameters is
Figure G2008100717837D00031
Figure G2008100717837D00032
β=90.980 °
Figure G2008100717837D00034
D c=4.713g/cm 3
The Nd that grows 3+: Li 3Ba 2La 3(MoO 4) 8Crystal carries out the analytical test of absorption spectrum, fluorescence spectrum and fluorescence lifetime etc., and the result shows: mix 4.4at.%Nd 3+The Nd of ion 3+: Li 3Ba 2La 3(MoO 4) 8The main absorption peak of crystal is at 804nm, and its peak width at half height is 7nm, and the absorption jump cross section is 11.4 * 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 804nm place, be conducive to laser crystals to the absorption of pump light, improve pumping efficiency.It has the emission band of three non-constant widths at the 850nm-1400nm wave band, wherein the peak width at half height (FWHM) of 1070nm place emission peak is 15nm, fluorescence lifetime is 0.135ms, because the crystal that fluorescence lifetime is long can accumulate more particle at last energy level, increase energy storage, be conducive to the raising of device output rating and output energy.Therefore, Nd 3+: Li 3Ba 2La 3(MoO 4) 8Crystal can obtain the output of more powerful laser, 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.
Nd 3+: Li 3Ba 2La 3(MoO 4) 8Crystal can grow superior in quality crystal easily with molten-salt growth 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 1.06 μ m, and this crystal can be used as a kind of laser crystals preferably.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 1.06 μ m wavelength around.The solid statelaser made from this crystal is used for spectroscopy, biomedicine, military field.
Embodiment
Realize that experiment optimal way of the present invention is as follows:
Embodiment 1: the flux growth doping content is 5.0at.%Nd 3+Nd 3+: Li 3Ba 2La 3(MoO 4) 8Laser crystals.Growth raw material is Li 3Ba 2La 3(MoO 4) 8: Li 2MoO 4=1:4 (mol ratio) mixes the Nd of 5at% 3+Ion.Adopt the fused salt top-seeded solution growth, in φ 60 * 50mm platinum alloy crucible, growth temperature is between 750 ~ 900 ℃, and with 1 ℃/day rate of temperature fall, 10 rev/mins crystal rotating speed has grown and has been of a size of 30 * 30 * 10mm 3High-quality Nd 3+: Li 3Ba 2La 3(MoO 4) 8Crystal.Nd in ICP (plasma emission spectrum) analysis revealed crystal 3+Ion content 4.4at%.

Claims (4)

1. neodymium-doped lanthanum barium lithium molybdate laser crystal, it is characterized in that: the molecular formula of this crystal is Nd 3+: Li 3Ba 2La 3(MoO 4) 8, belong to oblique system, have the C2/c spacer, unit cell parameters is
Figure FSB00001052047000011
D c=4.713g/cm 3, Nd 3+Ion is doped in the crystal as the laser active ion, replaces La in the crystal 3+The crystallographic site of ion, its doping content is between 0.5at.-15at.%.
2. the preparation method of the described neodymium-doped lanthanum barium lithium molybdate laser crystal of claim 1 is characterized in that: this crystal by adopting fused salt top-seeded solution growth growth, used fusing assistant is Li 2MoO 4, concentration is controlled between 60at~80at%, and growth temperature is between 750~900 ℃, and rate of temperature fall is 0.5~2 ℃/day, and rotating speed is 5~30rpm.
3. the purposes of the described neodymium-doped lanthanum barium lithium molybdate laser crystal of claim 1, it is characterized in that: this crystal is used for solid statelaser as working-laser material, use photoflash lamp or laser diode as pumping source, excite the laser output that produces 1.06 mum wavelengths.
4. the purposes of neodymium-doped lanthanum barium lithium molybdate laser crystal as claimed in claim 3 is characterized in that: the solid statelaser made from this crystal is used for spectroscopy, biomedicine, military field.
CN 200810071783 2008-09-16 2008-09-16 Neodymium-doped lanthanum barium lithium molybdate laser crystal and preparation method and application thereof Expired - Fee Related CN101676446B (en)

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CN102191551B (en) * 2010-03-10 2015-09-16 中国科学院福建物质结构研究所 Neodymium-doped potassium barium gadolinium molybdate crystals and its production and use
CN108505110B (en) * 2018-04-08 2019-10-22 中国科学院理化技术研究所 Tirubidium titanium germanate lithium compound, Tirubidium titanium germanate lithium nonlinear optical crystal, and preparation method and application thereof
CN113249790B (en) * 2021-05-26 2023-02-03 曲阜师范大学 Neodymium activated ion doped Na5Lu (MoO 4) 4 crystal and preparation method and application thereof

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CN1473966A (en) * 2002-08-08 2004-02-11 中国科学院福建物质结构研究所 Nd doped yttrium-barium borate laser crystal and its preparing method and use
CN1683609A (en) * 2004-04-13 2005-10-19 中国科学院福建物质结构研究所 Neodymium doped lithium lanthanum tungstate lacer crystla and its prepn
CN1916244A (en) * 2005-08-15 2007-02-21 中国科学院福建物质结构研究所 Laser crystal of lithium lanthanum molybdate with neodymium being doped, preparation method and usage
CN101063231A (en) * 2006-04-25 2007-10-31 中国科学院福建物质结构研究所 Chromium doped molybdic acid aluminum potassium tunable laser crystal

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1473967A (en) * 2002-08-08 2004-02-11 中国科学院福建物质结构研究所 Nd doped withe scandium-strontium-yttrium borate laser crystal and its preparing method and use
CN1473966A (en) * 2002-08-08 2004-02-11 中国科学院福建物质结构研究所 Nd doped yttrium-barium borate laser crystal and its preparing method and use
CN1683609A (en) * 2004-04-13 2005-10-19 中国科学院福建物质结构研究所 Neodymium doped lithium lanthanum tungstate lacer crystla and its prepn
CN1916244A (en) * 2005-08-15 2007-02-21 中国科学院福建物质结构研究所 Laser crystal of lithium lanthanum molybdate with neodymium being doped, preparation method and usage
CN101063231A (en) * 2006-04-25 2007-10-31 中国科学院福建物质结构研究所 Chromium doped molybdic acid aluminum potassium tunable laser crystal

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