CN100540755C - Efficient radioprotective Yb 3+Sensitization Er 3+Contain scandium garnet laser crystals and preparation method thereof - Google Patents

Efficient radioprotective Yb 3+Sensitization Er 3+Contain scandium garnet laser crystals and preparation method thereof Download PDF

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CN100540755C
CN100540755C CNB2007100222558A CN200710022255A CN100540755C CN 100540755 C CN100540755 C CN 100540755C CN B2007100222558 A CNB2007100222558 A CN B2007100222558A CN 200710022255 A CN200710022255 A CN 200710022255A CN 100540755 C CN100540755 C CN 100540755C
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sensitization
efficient
radioprotective
laser
laser crystals
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CN101063228A (en
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孙敦陆
殷绍唐
张庆礼
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Anhui Institute of Optics and Fine Mechanics of CAS
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Anhui Institute of Optics and Fine Mechanics of CAS
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Abstract

The invention belongs to a kind of efficient radioprotective Yb 3+Sensitization Er 3+Contain the scandium garnet laser crystals, it is characterized in that: this crystalline molecular formula is Yb 3+, Er 3+: A 3Sc 2B 3O 12[A=Gd, Y, Lu; B=Ga, Al], Yb 3+And Er 3+All be the A that replaces the dodecahedron central position 3+, Yb 3+Give active ions Er as sensitized ions with the transmission ofenergy that absorbs 3+, pass through Er 3+The low-mix and the height of ionic concn are mixed, and its laser wavelength is respectively near 1.5 μ m and 2.7-3 μ m.The laser of these two kinds of wave bands has important use in fields such as medical treatment, optical communication, scientific research and military affairs.Remove the needs that can satisfy general application, also can satisfy the needs that space environment is used.

Description

Efficient radioprotective Yb 3+Sensitization Er 3+Contain scandium garnet laser crystals and preparation method thereof
Technical field
The invention belongs to the functional crystal material field, a kind of specifically efficient radioprotective contains scandium garnet class laser crystals.
Technical background
In space science research, laser apparatus may be subjected to the irradiation of gamma-rays and high energy particle, thereby require the laser apparatus can antiradiation and resist the impact of high energy particle, therefore efficient radioprotective laserable material has great importance for the development of space laser technology.
Contain scandium garnet crystal A 3Sc 2B 3O 12[A=Gd, Y, Lu; B=Ga, Al] be the laser work matrix of excellent property, crystalline structure belongs to isometric system, can adopt the melt Czochralski grown to go out the monocrystalline of high optical quality.People such as Danileiko (Yu.K.Danileko et al.Sov.J.Quantum Electron., 1985,15:286) reported Nd, Cr:GSGG (Gd 3Sc 2Ga 3O 12Even) when surpassing 100Mrad, gamma-rays dosage do not reach its damage threshold yet, and Nd:YAG (Y 3Al 5O 12) laser apparatus is after being subjected to the gamma-ray irradiation of 1Mrad, its laser is exported the order of magnitude that descended.Because in containing the scandium garnet crystal, the Sc atom that is arranged in octahedra oxygen coordination center is compared with the Al atom with the Ga of GGG, YAG crystal same position, have the higher covalency characteristics and the order of key, the ability that opposing forms colour center strengthens, and therefore has the anti-ability of penetrating of strong spoke.It is a kind of strong radiation resistance material that this explanation contains the scandium garnet crystalloid, be more suitable in space environment, using than YAG,
Er 3+Ionic 1.5 μ m and 2.7-3 mu m waveband laser have important use in fields such as medical treatment, optical communication, scientific research and military affairs.But singly mixing Er 3+Laserable material in because Er 3+A little less than the absorption of InGaAs laser diode emission wavelength (0.9-1.1 μ m), influenced pumping efficiency.In order to improve pumping efficiency, to Er 3+It is necessary that ion carries out sensitization.Because Yb 3+Can effectively be coupled with the InGaAs emission wavelength, have more by force to absorb, and Yb 3+( 2F 5/2) emission band and Er 3+( 4I 11/2) absorption have bigger overlappingly, make Yb 3+Can be to Er 3+Carry out effective sensitization, the energy that absorbs is transferred to Er 3+Ion can reach the purpose of raising to pump light absorption efficiency and reduction laser generation threshold value.In recent years, the ripe and commercialization of the manufacturing technology of InGaAs940nm High power laser diode array is because Yb 3+Ion not only has also broad of big absorption cross but also absorption band in the 940nm vicinity, do not need the temperature of strict control laser diode, thereby can reduce the complexity of laser apparatus greatly, and helping device miniaturization, this is very important for the application in space science.Because matrix A 3Sc 2B 3O 12Itself has radiation-resisting functional, thus Yb, Er:A 3Sc 2B 3O 12Crystal is a kind of efficient radiation-resistant laserable material, removes the needs that can satisfy general application, also especially is fit to the needs that space environment is used.
In the seventies and eighties in last century, because Sc at that time 2O 3Raw material is very expensive, contains the research and development of scandium garnet crystalline thereby limited.In recent years, along with developing rapidly of application demand and extractive technique, Sc 2O 3Price reduction has by a relatively large margin been arranged.So, in the last few years, contained the research of scandium garnet crystalline abroad and rose again.According to the retrieval, at present both at home and abroad all also not about Yb, Er:A 3Sc 2B 3O 12Class contains scandium garnet crystalline report.
Summary of the invention
The objective of the invention is to disclose a kind of efficient radioprotective Yb that can realize efficient laser output at 1.5 μ m and 2.7-3 μ m 3+Sensitization Er 3+Contain scandium garnet laser crystals and preparation method thereof
Technical scheme of the present invention:
Efficient radioprotective Yb 3+Sensitization Er 3+Contain the scandium garnet laser crystals, it is characterized in that: this crystalline molecular formula is Yb 3+, Er 3+: A 3Sc 2B 3O 12[A=Gd, Y, Lu; B=Ga, Al], Yb 3+Give active ions Er as sensitized ions with the transmission ofenergy that absorbs 3+, pass through Er 3+The low-mix and the height of ionic concn are mixed, and its laser wavelength is respectively near 1.5 μ m and 2.8 μ m.
Yb wherein 3+Replacement concentration be 1-10at%, Er 3+Replacement concentration be 0.5-3at% or for 30-50at%.
This crystal except that the pump mode pumping of available routine, also can use wavelength as the semiconductor laser of 940-980nm as pumping source.
Described efficient radioprotective Yb 3+Sensitization Er 3+The method for preparing solid phase that contains the scandium garnet polycrystal raw material, it is characterized in that, according to following chemical equation:
3xYb 2O 3+ 3yEr 2O 3+ 3 (1-x-y) A 2O 3+ 2Sc 2O 3+ 3B 2O 3=2Yb 3xEr 3yA (3-3x-3y)Sc 2B 3O 12, A=Gd wherein, Y, Lu; B=Ga, Al, x=1-10%, y=0.5-3at% or 30-50at% make Yb by solid reaction process, Er:A 3Sc 2B 3O 12Polycrystal raw material.
Described efficient radioprotective Yb 3+Sensitization Er 3+The preparation method who contains the scandium garnet polycrystal raw material, it is characterized in that: also can adopt liquid phase method to make Yb, Er:A 3Sc 2B 3O 12Polycrystal raw material, liquid phase method refer to coprecipitation method or sol-gel method.
Described efficient radioprotective Yb 3+Sensitization Er 3+Contain scandium garnet laser crystals preparation method, it is characterized in that: use Yb, Er:A 3Sc 2B 3O 12Polycrystal raw material adopts melting method to prepare Yb, Er:A 3Sc 2B 3O 12Monocrystalline.
Yb, Er:A 3Sc 2B 3O 12Class contains scandium garnet and adopts the melt method for growing monocrystalline usually, and this method can grow larger-size monocrystalline with practical value; Also can adopt method preparations such as hydrothermal method.
The invention provides a kind of efficient radioprotective Yb 3+Sensitization Er 3+Ionic A 3Sc 2B 3O 12(wherein A can be rare earth ion Gd 3+, Y 3+Or Lu 3+, B can be Ga 3+Or Al 3+) class contains the scandium garnet laser crystals, crystalline structure belongs to isometric system, can adopt the melt Czochralski grown to go out the crystal of high optical homogeneity.A 3Sc 2B 3O 12It is a kind of strong radiation resistance material that class contains the scandium garnet crystal, is more suitable for using in space environment than YAG.Because Yb 3+Can effectively be coupled with InGaAs emission wavelength (0.9-1.1 μ m), have more by force to absorb, and Yb 3+( 2F 5/2) emission band and Er 3+( 4I 11/2) absorption have bigger overlappingly, make Yb 3+Can be to Er 3+Carry out effective sensitization, the energy that absorbs is transferred to Er 3+Ion can reach the purpose that improves pump light absorption efficiency and reduce the laser generation threshold value.Therefore, Yb, Er:A 3Sc 2B 3O 12Crystal is expected to become a kind of LD pumping and is fit to the efficient laser crystals that use in the space.Use Yb, Er:A 3Sc 2B 3O 12Crystalline 1.5 μ m and 2.7-3 mu m waveband laser have important use in fields such as medical treatment, optical communication, scientific research and military affairs.Remove the needs that can satisfy general application, also can satisfy the needs that space environment is used.
Description of drawings
Fig. 1 adopts semiconductor laser to realize Yb as pumping source, Er:GSGG (Gd 3Sc 2Ga 3O 12) a kind of Experimental equipment of crystal laser output.
Embodiment
Embodiment 1: growth low-mix Er 3+The Yb of ionic concn, Er:GSGG (Gd 3Sc 2Ga 3O 12) crystal
Low-mix Er 3+The Yb of ionic concn, the Er:GSGG crystal is meant Er 3+The ionic doping content between 0.5-3at%, the laser of its exportable 1.5 μ m, the polycrystal raw material with solid phase method or liquid phase method preparation adopts the melt crystal pulling method can grow low-mix Er 3+Yb, the Er:GSGG single crystal.
Embodiment 2: the growth height is mixed Er 3+The Yb of ionic concn, Er:GSGG (Gd 3Sc 2Ga 3O 12) crystal
Height is mixed Er 3+The Yb of ionic concn, the Er:GSGG crystal is meant Er 3+The ionic doping content between 30-50at%, the laser of its exportable 2.8 μ m, the polycrystal raw material with solid phase method or liquid phase method preparation adopts the melt crystal pulling method can grow height and mixes Er 3+Yb, the Er:GSGG single crystal.
Embodiment 3: realize Yb, Er:GSGG (Gd 3Sc 2Ga 3O 12) near a kind of experimental installation of laser output crystal 1.5 mu m wavebands
Adopt 940nm diode-end-pumped Yb, Er:GSGG (Yb 3+Doping content be 1-10at%, Er 3+Doping content be 0.5-3at%) crystal element.Experimental installation such as accompanying drawing 1.1 is Yb among the figure, the Er:GSGG crystal element; The 2nd, the 940nm semiconductor laser; The 3rd, near the wavelength total reflection 1.5 μ m to the dielectric mirror of 940nm total transmissivity; The 4th, near the wavelength part transmission 1.5 μ m to the dielectric mirror of 940nm total reflection; The 5th, the LPE-1A laser energy meter; The 6th, condenser lens.
Embodiment 4: realize Yb, Er:GSGG (Gd 3Sc 2Ga 3O 12) near a kind of experimental installation of the laser output crystal 2 .8 mu m waveband
Adopt 940nm diode-end-pumped Yb, Er:GSGG (Yb 3+Doping content be 1-10at%, Er 3+Doping content be 30-50at%) crystal element.Experimental installation such as accompanying drawing 1.1 is Yb among the figure, the Er:GSGG crystal element; The 2nd, the 940nm semiconductor laser; The 3rd, near the wavelength total reflection 2.8 μ m to the dielectric mirror of 940nm total transmissivity; The 4th, near the wavelength part transmission 2.8 μ m to the dielectric mirror of 940nm total reflection; The 5th, the LPE-1A laser energy meter; The 6th, condenser lens.Because wavelength is in the strong absorption band of water near the 2.8 μ m, therefore in this Laser Experiments device, also needs to get rid of the aqueous vapor in the resonator cavity or shorten resonator cavity to reduce the detrimentally affect of aqueous vapor to laser generation.

Claims (5)

1, efficient radioprotective Yb 3+Sensitization Er 3+Contain the scandium garnet laser crystals, it is characterized in that: this crystalline molecular formula is Yb 3+, Er 3+: A 3Sc 2B 3O 12, A=Gd, Y, Lu; B=Ga, Al, Yb 3+Give active ions Er as sensitized ions with the transmission ofenergy that absorbs 3+, pass through Er 3+The low-mix and the height of ionic concn are mixed, and its laser wavelength is respectively at 1.5 μ m and 2.7-3 μ m, wherein Yb 3+Replacement concentration be 1-10at%, Er 3+Replacement concentration be 0.5-3at% or for 30-50at%.
2, efficient radioprotective Yb as claimed in claim 1 3+Sensitization Er 3+Contain the scandium garnet laser crystals, it is characterized in that: this crystal except that the pump mode pumping of available routine, also can use wavelength as the semiconductor laser of 940-980nm as pumping source.
3, efficient radioprotective Yb according to claim 1 3+Sensitization Er 3+The preparation method who contains the scandium garnet laser crystals, it is characterized in that: efficient radioprotective Yb 3+Sensitization Er 3+The method for preparing solid phase that contains the scandium garnet polycrystal raw material according to following chemical equation:
3xYb 2O 3+ 3yEr 2O 3+ 3 (1-x-y) A 2O 3+ 2Sc 2O 3+ 3B 2O 3=2Yb 3xEr 3yA (3-3x-3y)Sc 2B 3O 12, A=Gd wherein, Y, Lu; B=Ga, Al, x=1-10%, y=0.5-3at% or 30-50at% make Yb by solid reaction process, Er:A 3Sc 2B 3O 12Polycrystal raw material.
4, efficient radioprotective Yb according to claim 1 3+Sensitization Er 3+The preparation method who contains the scandium garnet laser crystals, it is characterized in that: adopt liquid phase method to make Yb, Er:A 3Sc 2B 3O 12Polycrystal raw material, liquid phase method refer to coprecipitation method or sol-gel method.
5, efficient radioprotective Yb according to claim 1 3+Sensitization Er 3+The preparation method who contains the scandium garnet laser crystals, it is characterized in that: use Yb, Er:A 3Sc 2B 3O 12Polycrystal raw material adopts melting method to prepare Yb, Er:A 3Sc 2B 3O 12Monocrystalline.
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CN102127813A (en) * 2010-12-27 2011-07-20 中国科学院安徽光学精密机械研究所 High-efficiency mid-infrared laser crystal Pr, Er:YSGG and preparation method thereof
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