CN101597797B - Ytterbium-doped lithium gadolinium borate laser crystal and preparation method thereof - Google Patents

Ytterbium-doped lithium gadolinium borate laser crystal and preparation method thereof Download PDF

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CN101597797B
CN101597797B CN2009100542131A CN200910054213A CN101597797B CN 101597797 B CN101597797 B CN 101597797B CN 2009100542131 A CN2009100542131 A CN 2009100542131A CN 200910054213 A CN200910054213 A CN 200910054213A CN 101597797 B CN101597797 B CN 101597797B
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crystal
raw material
ytterbium
doped lithium
crystal growth
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CN101597797A (en
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潘尚可
杨帆
任国浩
丁栋舟
陆晟
张卫东
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention discloses an ytterbium-doped lithium gadolinium borate laser crystal and a preparation method thereof. The chemical formula of the ytterbium-doped lithium gadolinium borate laser crystal is Li6YbxGd1-xB3O9, wherein, x is more than 0 and is 0.3 at most. The invention also provides a preparation method of the ytterbium-doped lithium gadolinium borate laser crystal, comprising the following steps: selecting crystal growing raw materials, synthesizing the crystal growing raw materials and preparing single crystal by a crystal pulling method. The ytterbium-doped lithium gadolinium borate laser crystal of the invention has larger adsorption half-peak width and emission half-peak width, and is favourable for outputting LD pump Laser and producing ultra-fast laser pulse; the ytterbium-doped lithium gadolinium borate laser crystal is a novel and potential ultra-fast laser crystal which provides favourable basis for engineering application.

Description

Ytterbium-doped lithium gadolinium borate laser crystal and preparation method thereof
Technical field
The present invention relates to the laser crystals field, be specifically related to a kind of Ytterbium-doped lithium gadolinium borate laser crystal and preparation method thereof.
Background technology
Along with succeeding in developing of ti sapphire laser, femtosecond and Tunable Laser Technology have obtained to use widely in scientific research.But the structure of the complicacy of ti sapphire laser and huge volume have limited it in industrial application.The nineties in 20th century, goal in research concentrates on the Cr:LiSAF crystal, and the laser apparatus made from its has compact construction, volume is little and efficient is high advantage, but its laser output power is big inadequately, and range of application also possibly be confined to the biomedical imaging field.Recently, mix Yb at several kinds 3+Realized femtosecond pulse output in the ionic laser crystals, wherein Yb:Sr 3Y (BO 3) 3It is that 80mw, PW are the femtosecond pulse output of 69fs that crystal has obtained mean power.Therefore, explore the small volume, portable of novel suitable industrial application, can enough LD pumpings mix Yb 3+Ion ultrafast laser crystal becomes a new focus of laserable material research.
Mix Yb 3+The research of ion laser crystalline is along with the development of high-power InGaAs semiconductor laser comes into one's own day by day.As laser active ion, Yb 3+Ion has following characteristics:
1) Yb 3+Ion is the simplest rare earth activation ion of energy level, and electronic configuration is [Xe] 4f 13, a ground state is only arranged 2F 7/2With an excited state 2F 5/2, both energy level spacings are 10000cm -1, under the crystal field effect, can produce Stark splitting, form the laser operating mechanism of quasi-three-level.
2) Yb 3+The ionic absorption band can effectively be coupled with InGaAs LD in 0.9～1.0 mum wavelength scope, and it is wide to absorb peak width at half (FWHM), need not strict temperature control condition.
3) the quantum loss is low, and pumping wavelength and laser output wavelength are very approaching, and this will cause the big oblique efficient of intrinsic laser, and its quantum yield is up to about 90% in theory.
4) fluorescence lifetime is long, is generally to mix Nd 3+2～3 times of ion laser material, the long life-span helps energy storage.
5), thereby avoided unnecessary power losses such as excited state absorption, concentration quenching and last conversion owing to have only two energy levels, and the very high Yb that can mix 3+Ionic concn.
Therefore, with the Yb that mixes of LD pumping 3+Ion laser has very high efficient, and it can be used for developing high power laser, micro-slice laser and green self-frequency-doubling laser.Because Yb 3+Ionic outermost electron structure is 4f 13, having bigger spin-orbit coupling coefficient, its emission live width is wide especially, can also be as tunable and operation material femto-second laser.That realize femtosecond pulse output at first is Yb:YAG crystal and Yb:glass.Crystal has machinery and thermal property preferably with respect to glass, mixes Yb and become 3+The ionic optimum substrate.Recently, Yb:Sr 3Y (BO 3) 3It is 80mW that laser crystals has obtained mean power, and PW is the femtosecond pulse output of 69fs, and this is to mix Yb up to now 3+The short pulse of realizing in the ionic laser crystals.
Lithium gadolinium borate, its compound chemistry formula is Li 6GdB 3O 9, on the gadolinium ion case, mix cerium ion, can be used as the neutron detection crystalline material.Equally, this crystal also can mix ytterbium ion on the gadolinium ion case, as laser crystal material.As a kind of Ytterbium-doped lithium gadolinium borate laser crystal material, Li 6Yb xGd 1-xB 3O 9Laser crystals both can be realized the LD pumping; Can be used as a kind of crystalline material that can produce ultrafast laser pulse output again; Therefore can expect that this laser crystals can be widely used in industrial aspect, yet in the prior art, also considerably less to the report of this type of laser crystals.
Summary of the invention
The invention provides a kind of Ytterbium-doped lithium gadolinium borate laser crystal and preparation method thereof, this Ytterbium-doped lithium gadolinium borate laser crystal can be applicable to laser field, can use the LD laser pumping, can also be used to produce the ultrafast laser pulse.
To achieve these goals, the technical scheme of the present invention's employing is following:
A kind of Ytterbium-doped lithium gadolinium borate laser crystal, this crystalline chemical formula is: Li 6Yb xGd 1-xB 3O 9, wherein x is Yb 3+Doping content, and the span of x is 0＜x≤0.3.
The preparation method of Ytterbium-doped lithium gadolinium borate laser crystal of the present invention comprises the steps:
1) joining of crystal growth raw material gets: be mixed into admixtion behind the various raw materials of weighing in proportion;
2) the crystal growth raw material is synthetic: sintering made the crystal growth raw material after admixtion was pressed into the material piece;
3) single crystal preparation: the crystal growth raw material is heated to abundant fusing, obtains the crystal growth melt, adopt crystal pulling method to carry out crystal growth and obtain Ytterbium-doped lithium gadolinium borate laser crystal.
This preparation method is specially:
1) joining of crystal growth raw material gets:
According to chemical formula Li 6Yb xGd 1-xB 3O 9In be mixed into admixtion behind the various raw materials of stoichiometric ratio weighing of each component;
2) the crystal growth raw material is synthetic:
The admixtion for preparing in the step 1) is pressed into material puts into the corundum cup behind the piece, place retort furnace, be warmed up to 440～460 ℃, sintering is after 9～11 hours, cooling; After the taking-up, grind, be pressed into the material piece once more, put into retort furnace, be warming up to 650～750 ℃, sintering was lowered the temperature after 9 to 11 hours;
3) single crystal preparation:
The raw material that sinters is inserted in the crucible, put into lifting furnace, be heated to abundant fusing, obtain the crystal growth melt; Then with platinum wire or lithium gadolinium borate monocrystalline as crystal growth seed crystal, take crystal pulling method to grow.
Raw material in the said step 1) comprises: contain Li element raw material, contain B element raw material, contain Gd element raw material and contain Yb element raw material.
Preferably, the said Li of containing element raw material is selected from Li 2CO 3With among the LiOH one or more; Contain B element raw material and be selected from H 3BO 3And B 2O 3In one or more; Containing Gd element raw material is Gd 2O 3Containing Yb element raw material is Yb 2O 3
Preferably, in the said step 1), contain the weight of B element raw material excessive 1～5% (that is: contain the weight that contains B element raw material excessive 1～5% that the weight ratio of B element raw material is calculated according to the stoichiometric ratio of B element in the chemical formula).
Preferably, the material block is a right cylinder material block said step 2).
Preferably, when said step 3) adopted crystal pulling method to carry out crystal growth, crystal growth temperature was 800～865 ℃, and rotating speed is 1～10rpm during crystal growth, and pulling rate is 0.1～2mm/h, and rate of temperature fall is 0.4～0.8 ℃/h.
Preferably, when said step 3) adopts crystal pulling method to carry out crystal growth, crystal growth at air, nitrogen, argon gas, contain the nitrogen of oxygen 1～10at.% or contain in the atmosphere of argon gas of oxygen 1～10at.% and carry out.
Preferably, when adopting crystal pulling method to carry out crystal growth in the said step 3), as crystal growth seed crystal, and lithium gadolinium borate seed crystal direction can be any with platinum wire or lithium gadolinium borate monocrystalline.
Preferably, the crucible in the said step 3) is platinum crucible or Iridium Crucible.
The present invention has prepared a kind of Li that is applied to laser field through crystal pulling method 6Yb xGd 1-xB 3O 9Laser crystals, this crystal have bigger absorption peak width at half (67nm) and emission peak width at half (57nm), are 5.7 * 10 at the absorption cross of 969nm wavelength -21Cm 2, be 3.9 * 10 at the emission cross section of 1020nm wavelength -21Cm 2This crystal absorbs peak width, helps the output of LD pumping laser.Simultaneously, this crystal has very wide emission peak (57nm), helps producing the ultrafast laser pulse, is the novel ultrafast laser crystal of a kind of potential.Li of the present invention 6Yb xGd 1-xB 3O 9Laser crystals can be used the LD laser pumping, can also be used to produce the ultrafast laser pulse, and using for through engineering approaches provides good basis.
Description of drawings
The Li of Fig. 1 the present invention preparation 6Yb 0.1Gd 0.9B 3O 9Crystalline absorbs the synoptic diagram that concerns of (emission) cross section and wavelength.
Embodiment
Further describe Ytterbium-doped lithium gadolinium borate laser crystal of the present invention and preparation method thereof through specific embodiment below.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.
Embodiment 1
According to chemical formula is Li 6Yb 0.1Gd 0.9B 3O 9(x=0.1) Ytterbium-doped lithium gadolinium borate laser crystal, concrete steps are following:
1, presses in the chemical formula each component metering than weighing Li 2CO 3(purity is 99.99%) 77.59g, Gd 2O 3(purity is 99.99%) 57.09g, B 2O 3(purity is 99.99%) 36.92g and Yb 2O 3(purity is 99.99%) 6.90g is mixed into admixtion with above-mentioned raw materials;
2, the admixtion that mixes is pressed into the cylindric bulk that diameter is 50mm, puts into the corundum cup,, take out, grind again, be pressed into bulk again, insert in the retort furnace, 700 ℃ of following sintering 10 hours 450 ℃ of sintering temperatures 10 hours;
3, it is the Iridium Crucible of 60mm that the raw material after sintering is accomplished places diameter, is seed crystal with pure lithium gadolinium borate monocrystalline, and rotating speed is 5rpm, and pulling rate is 0.5mm/h, and crystal growth temperature is 800 ℃, and rate of temperature fall is: 0.6 ℃/h.Through 3 days growth, can grow diameter was 25mm in air atmosphere, and length is the monocrystalline about 30mm.
The monocrystalline performance test results: this crystal has bigger absorption peak width at half (67nm) and emission peak width at half (57nm), and fluorescence lifetime is 2.8ms.Absorption cross in the 969nm wavelength is 5.7 * 10 -21Cm 2, be 3.9 * 10 at the emission cross section of 1020nm wavelength -21Cm 2This crystal absorbs peak width, helps the output of LD pumping laser, and the relation of this crystalline absorption cross and emission cross section and wavelength is as shown in Figure 1.Simultaneously, this crystalline emission peak also very wide (57nm) helps producing the ultrafast laser pulse, is the novel ultrafast laser crystal of a kind of potential.
Embodiment 2
According to chemical formula is Li 6Yb 0.01Gd 0.99B 3O 9(x=0.01) Ytterbium-doped lithium gadolinium borate laser crystal, concrete steps are following:
1, measures than weighing LiOH (purity is 99.99%) 50.29g, Gd by each component in the chemical formula 2O 3(purity is 99.99%) 62.80g, B 2O 3(purity is 99.99%) 36.92g and Yb 2O 3(purity is 99.99%) 0.69g is mixed into admixtion with above-mentioned raw materials;
2, the admixtion that mixes is pressed into the cylindric bulk that diameter is 50mm, puts into the corundum cup,, take out, grind again, be pressed into bulk again, insert in the retort furnace, 650 ℃ of following sintering 10 hours 450 ℃ of sintering temperatures 10 hours;
3, it is the Iridium Crucible of 60mm that the raw material after sintering is accomplished places diameter, is seed crystal with the platinum wire, and rotating speed is 1rpm, and pulling rate is 0.1mm/h, and crystal growth temperature is 845 ℃, and rate of temperature fall is: 0.4 ℃/h.Through 3 days growth, can grow diameter was 25mm in the nitrogen atmosphere that contains oxygen 1at.%, and length is the monocrystalline about 30mm.
Embodiment 3
According to chemical formula is Li 6Yb 0.3Gd 0.7B 3O 9(x=0.3) Ytterbium-doped lithium gadolinium borate laser crystal, concrete steps are following:
1, presses in the chemical formula each component metering than weighing Li 2CO 3(purity is 99.99%) 50.29g, Gd 2O 3(purity is 99.99%) 44.41g, H 3BO 3(purity is 99.99%) 65.57g and Yb 2O 3(purity is 99.99%) 20.69g is mixed into admixtion with above-mentioned raw materials;
2, the admixtion that mixes is pressed into the cylindric bulk that diameter is 50mm, puts into the corundum cup,, take out, grind again, be pressed into bulk again, insert in the retort furnace, 750 ℃ of following sintering 10 hours 450 ℃ of sintering temperatures 10 hours;
3, it is the Iridium Crucible of 60mm that the raw material after sintering is accomplished places diameter, is seed crystal with the lithium gadolinium borate monocrystalline, and rotating speed is 10rpm, and pulling rate is 2mm/h, and crystal growth temperature is 865 ℃, and rate of temperature fall is: 0.8 ℃/h.Through 3 days growth, can grow diameter was 25mm in the argon gas atmosphere that contains oxygen 10at.%, and length is the monocrystalline about 30mm.

Claims (8)

1. Ytterbium-doped lithium gadolinium borate laser crystal, this crystalline chemical formula is: Li 6Yb xGd 1-xB 3O 9, and the span of x is 0＜x≤0.3.
2. the preparation method of the said Ytterbium-doped lithium gadolinium borate laser crystal of claim 1 comprises the steps:
1) joining of crystal growth raw material gets: be mixed into admixtion behind the various raw materials of weighing in proportion;
2) the crystal growth raw material is synthetic: sintering made the crystal growth raw material after admixtion was pressed into the material piece;
3) single crystal preparation: the crystal growth raw material is heated to abundant fusing; Obtain the crystal growth melt, adopt crystal pulling method to carry out crystal growth and obtain Ytterbium-doped lithium gadolinium borate laser crystal, when adopting crystal pulling method to carry out crystal growth; Crystal growth temperature is 800～865 ℃; Rotating speed is 1～10rpm during crystal growth, and pulling rate is 0.1～2mm/h, and rate of temperature fall is 0.4～0.8 ℃/h.
3. like the preparation method of the said Ytterbium-doped lithium gadolinium borate laser crystal of claim 2, it is characterized in that the raw material in the said step 1) comprises: contain Li element raw material, contain B element raw material, contain Gd element raw material and contain Yb element raw material.
4. like the preparation method of the said Ytterbium-doped lithium gadolinium borate laser crystal of claim 3, it is characterized in that the said Li of containing element raw material is selected from Li 2CO 3Or among the LiOH one or more; Contain B element raw material and be selected from H 3BO 3Or B 2O 3In one or more; Containing Gd element raw material is Gd 2O 3Containing Yb element raw material is Yb 2O 3
5. like the preparation method of the said Ytterbium-doped lithium gadolinium borate laser crystal of claim 3, it is characterized in that the said weight excessive 1～5% that contains B element raw material.
6. like the preparation method of the said Ytterbium-doped lithium gadolinium borate laser crystal of claim 2, it is characterized in that said step 2) in the synthesis step of crystal growth raw material be: admixtion is pressed into sintering behind the material piece, cooling and grind after be pressed into material piece sintering once more, cooling.
7. like the preparation method of the said Ytterbium-doped lithium gadolinium borate laser crystal of claim 2; It is characterized in that; When said step 3) adopts crystal pulling method to carry out crystal growth, crystal growth at air, nitrogen, argon gas, contain the nitrogen of oxygen 1～10at.% or contain in the atmosphere of argon gas of oxygen 1～10at.% and carry out.
8. like the preparation method of the said Ytterbium-doped lithium gadolinium borate laser crystal of claim 2, it is characterized in that, when adopting crystal pulling method to carry out crystal growth in the said step 3), with platinum wire or lithium gadolinium borate monocrystalline as crystal growth seed crystal.
CN2009100542131A 2009-06-30 2009-06-30 Ytterbium-doped lithium gadolinium borate laser crystal and preparation method thereof Expired - Fee Related CN101597797B (en)

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CN101864596A (en) * 2010-07-02 2010-10-20 中国科学院上海光学精密机械研究所 Ytterbium-gadolinium codoped barium fluoride crystal and preparation method thereof
CN102337591B (en) * 2011-11-14 2013-09-25 西北大学 Ytterbium-doped potassium triyttrium borate laser crystal, and growing method and application thereof
CN103603034B (en) * 2013-11-07 2016-08-17 上海交通大学 A kind of method preparing large scale HTS single crystals body
CN104372410A (en) * 2014-11-17 2015-02-25 中国科学院上海硅酸盐研究所 Cerium-doped rare earth borate scintillation crystal and preparation method thereof
CN113930842A (en) * 2021-10-14 2022-01-14 上海应用技术大学 Preparation method of cerium-doped lithium lutetium borate crystal

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