CN103981574A - Pr3+ ions doped calcium, magnesium, zirconia, gadolinium and gallium garnet and melt method for crystal growth thereof - Google Patents

Pr3+ ions doped calcium, magnesium, zirconia, gadolinium and gallium garnet and melt method for crystal growth thereof Download PDF

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Publication number
CN103981574A
CN103981574A CN201410171413.6A CN201410171413A CN103981574A CN 103981574 A CN103981574 A CN 103981574A CN 201410171413 A CN201410171413 A CN 201410171413A CN 103981574 A CN103981574 A CN 103981574A
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crystal
ggg
growth
crystal growth
melt
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刘文鹏
张庆礼
殷绍唐
孙敦陆
孙贵华
罗建乔
王小飞
高进云
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Hefei Institutes of Physical Science of CAS
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Hefei Institutes of Physical Science of CAS
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Abstract

The present invention discloses visible laser crystals of a Pr3+ ions doped calcium, magnesium, zirconia, gadolinium and gallium garnet with broadband absorption and a melt method for the crystal growth of the garnet. The crystal has a molecular formula of Pr<3delta> Ca<3x>Gd<3(1-x-delta)>Mg<y>Zr<z>Ga<5(1-y-z)>O<12+delta-15x-2.5y+2.5z>, wherein 0 < x + delta < 1, 0 < y + z < 1. By adjusting the crystal components, an absorption bandwidth of Pr3 + ions is broadened, pumping efficiency within crystal visible band is improved. By adopting traditional crystal pulling method, crucible descent method, flux growth method and other melt method to carry out directional or non-directional crystal growth, the obtained crystals can be used as working substances for all solid state lasers. The present invention has broad application prospects in areas of laser display, laser communication, information storage and the like.

Description

Pr 3+the Ca, Mg, Zr, Gd and Ga garnet of ion doping and crystal growth method by melt method thereof
Technical field
The present invention relates to laserable material and field of crystal growth, specifically a kind of visible ray laser crystals Pr of wide band absorption 3+ion doping Ca, Mg, Zr, Gd and Ga garnet and crystal growth method by melt method thereof.
Technical background
All solid state visible light wave range laser is with a wide range of applications in various fields such as laser display, laser communication, information storage, laser medicine, material processing, is the focus of current all-solid state laser technical study.Owing to lacking efficient semiconductor diode (LD) pumping source, all solid state visible light wave range Laser Study is made slow progress before.Royal purple light LD has had very great development in recent years, and output rating improves rapidly, and price also declines thereupon, provides condition for realizing all solid state visible ray laser.Therefore the visible ray laserable material that, dominance can be suitable for royal purple light LD pump-coupling becomes the key that realizes all solid state visible ray Laser output.
Rare earth ion Pr 3+be a kind of visible ray light emitting ionic of excellence, there is near the VISIBLE LIGHT EMISSION transition of multiple wavelength such as 739nm, 711nm, 656nm, 617nm, 558nm, 493nm, and there is strong absorption at blue wave band, be suitable for blue light LD pumping.But Pr 3+ion exists the narrow shortcoming of absorption band, and simultaneously because the spectral width of LD is narrow, emission wavelength drifts about along with the variation of working temperature, and therefore LD is to Pr 3+the pumping efficiency of ion doping material is generally lower.But, Pr 3+ion is the trivalent rare earth ions the most responsive to substrate material crystal field, therefore, and by regulating substrate material crystal field, broadening Pr 3+ionic absorption band is the important channel of improving pumping efficiency.
(Ca, Mg, Zr) GGG crystal is a kind of good laser host material, and crystalline structure belongs to isometric system, can adopt melting method to prepare large size high optical quality monocrystalline.In (Ca, Mg, Zr) GGG crystal, Ca2 +occupy Ga 3+case, Mg 2+and Zr 4+occupy Gd 3+case.Change and the chaotic distribution of ion because interionic ionic radius difference causes crystal lattices constant, regulate by crystal composition, crystal field can be finely tuned.Therefore, Pr 3+absorber Bandwidth in (Ca, Mg, Zr) GGG crystal can obtain broadening, can obtain all solid state visible ray laserable material that high efficiency and broad band absorbs.
Summary of the invention
The object of the invention is to be openly a kind ofly suitable for blue light LD pumping, can regulate Absorber Bandwidth, realize the Pr:(Ca of efficient visible light Laser output, Mg, Zr) GGG crystal and crystal growth method by melt method thereof, obtain the laser crystals of large size high optical quality, as all solid state visible ray working-laser material.
Technical scheme of the present invention is:
Pr 3+the visible ray laser crystals Pr:(Ca of ion doping, Mg, Zr) GGG, it is characterized in that: the molecular formula of described crystal is Pr 3 δca 3xgd 30-x-δ)mg yzr zga 5d-y-z)o 12+ δ-1.5x-2.5y+2.5z, wherein 0<x+ δ <1,0<y+z<1, by regulating crystal composition, can effectively regulate crystal field strength, broadening light emitting ionic Pr 3+absorber Bandwidth, improve the laser pumping efficiency of crystal visible light wave range.
The laser crystals that described crystal is is matrix with (Ca, Mg, Zr) GGG crystal.
Described Pr:(Ca, Mg, Zr) crystal growth method by melt method of GGG crystal, it is characterized in that:
(1), Pr:(Ca, Mg, Zr) batching of GGG crystal growth raw material:
Adopt Pr 6o 11, Gd 2o 3, Ga 2o 3, CaO, MgO, ZrO 2as raw material, prepare burden by the mol ratio of following chemical formula, and fully mix:
(2), the compacting of raw material and sintering: the each feed composition mixing is suppressed with sintering and obtained crystal growth initial feed, sintering temperature is 1000-1600 DEG C, time is 10-72 hour, and the initial feed of also can growing the raw material after press forming as crystal is directly carried out crystal growth without sintering.
(3), crystal growth method by melt: the crystal initial feed of growing is put into growth crucible, by heating fully fusing, obtain crystal growth initial melt; Then adopt the crystal growth method by melt method such as crystal pulling method, falling crucible method, warm terraced method to grow.
Described Pr:(Ca, Mg, Zr) GGG growing method, it is characterized in that: for the melt-method growth process that need to adopt seed crystal oriented growth, seed crystal is Pr:(Ca, Mg, Zr) GGG monocrystalline, (Ca, Mg, Zr) GGG monocrystalline, or GGG monocrystalline, seed crystal direction is generally crystal [111] direction, and other any definite direction.
Described Pr:(Ca, Mg, Zr) GGG growing method, it is characterized in that: raw materials used Pr in described batching 6o 11, Gd 2o 3, Ga 2o 3, CaO, M go, ZrO 2adopt corresponding Pr 3+, Gd 3+, Ga 3+, Ca 2+, Mg 2+, Zr 4+other compound replace, can finally form Pr:(Ca, Mg, Zr by chemical reaction but need to meet) this condition of GGG compound.
Described Pr:(Ca, Mg, Zr) GGG growing method, it is characterized in that: consider the effect of segregation in crystal growing process, establish described Pr:(Ca, Mg, Zr) in GGG crystal, the segregation coefficient of certain element is k, k=0.01-1, in the time that the quality of the compound of this element in chemical combination formula in described (1) is W, should be adjusted into W/k in batching.
Pr:(Ca, Mg, Zr) GGG crystal can be used as the operation material of all solid state visible laser of blue light LD pumping.Host crystal of the present invention can make Pr 3+the absorption band broadening of ion, LD pumping efficiency improves.
Embodiment
Example 1, melt method for growing Pr:(Ca, Mg, Zr) GGG crystal
(1), Pr:(Ca, Mg, Zr) batching of GGG crystal growth raw material:
Adopt Pr 6o 11, Gd2O 3, Ga 2o 3, CaO, MgO, ZrO 2as raw material, prepare burden by the mol ratio of following chemical formula, and fully mix:
If the effect of segregation in consideration crystal growing process, if described Pr:(Ca, Mg, Zr) in GGG crystal, the segregation coefficient of certain element is k, k=0.01-1,, in the time that the quality of the compound of this element in chemical combination formula in described (1) is W, in batching, should be adjusted into W/k.
(2), the compacting of raw material and sintering:
The each feed composition mixing is suppressed with sintering and obtained crystal growth initial feed, sintering temperature is 1000-1600 DEG C, time is 10-72 hour, and the initial feed of also can growing the raw material after press forming as crystal is directly carried out crystal growth without sintering.
(3), crystal growth method by melt:
The crystal initial feed of growing is put into growth crucible, by heating fully fusing, obtain crystal growth initial melt; Then adopt the crystal growth method by melt method such as crystal pulling method, falling crucible method, warm terraced method to grow.For the melt-method growth process that need to adopt seed crystal oriented growth, seed crystal is Pr:(Ca, Mg, Zr) GGG monocrystalline, (Ca, Mg, Zr) GGG monocrystalline, or GGG monocrystalline, seed crystal direction is generally [111] direction of crystal, and other any definite direction.

Claims (5)

1.Pr 3+the Ca, Mg, Zr, Gd and Ga garnet visible ray laser crystals of ion doping, is characterized in that: the molecular formula of described crystal is Pr 35ca 3xgd 30-x-5)mg yzr zga 5 (1-y-z)o 12+ δ-1.5x-2.5y+2.5z, wherein 0<x+ δ <1,0<y+z<1, is abbreviated as Pr:(Ca, Mg, Zr) GGG.
2. Pr according to claim 1 3+the Pr:(Ca of ion doping, Mg, Zr) crystal growth method by melt method of GGG crystal, it is characterized in that:
(1), Pr:(Ca, Mg, Zr) batching of GGG crystal growth raw material:
Adopt Pr 6o 11, Gd 2o 3, Ga 2o 3, CaO, MgO, ZrO 2as raw material, prepare burden by the mol ratio of following chemical formula, and fully mix:
(2), the compacting of raw material and sintering: the each feed composition mixing is suppressed with sintering and obtained crystal growth initial feed, sintering temperature is 1000-1600 DEG C, time is 10-72 hour, and the initial feed of also can growing the raw material after press forming as crystal is directly carried out crystal growth without sintering;
(3), crystal growth method by melt: the crystal initial feed of growing is put into growth crucible, by heating fully fusing, obtain crystal growth initial melt; Then adopt the crystal growth method by melt method such as crystal pulling method, falling crucible method, warm terraced method to grow.
3. Pr:(Ca according to claim 2, Mg, Zr) GGG growing method, it is characterized in that: for the melt-method growth process that need to adopt seed crystal oriented growth, seed crystal is Pr:(Ca, Mg, Zr) GGG monocrystalline, (Ca, Mg, Zr) GGG monocrystalline, or GGG monocrystalline, seed crystal direction is generally crystal [111] direction, and other any definite direction.
4. Pr:(Ca according to claim 2, Mg, Zr) GGG growing method, it is characterized in that: raw materials used Pr in described batching 6o 11, Gd 2o 3, Ga 2o 3, CaO, MgO, ZrO 2adopt corresponding Pr 3+, Gd 3+, Ga 3+, Ca2 +, Mg 2+, Zr 4+other compound replace, can finally form Pr:(Ca, Mg, Zr by chemical reaction but need to meet) this condition of GGG compound.
5. Pr:(Ca according to claim 2, Mg, Zr) GGG growing method, it is characterized in that: consider the effect of segregation in crystal growing process, establish described Pr:(Ca, Mg, Zr) in GGG crystal, the segregation coefficient of certain element is k, k=0.01-1, in the time that the quality of the compound of this element in the chemical combination formula in described (1) is W, should be adjusted into W/k in batching.
CN201410171413.6A 2014-04-28 2014-04-28 Pr3+ ions doped calcium, magnesium, zirconia, gadolinium and gallium garnet and melt method for crystal growth thereof Pending CN103981574A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101476156A (en) * 2008-12-30 2009-07-08 中国科学院安徽光学精密机械研究所 Gadolinium, yttrium, scandium and gallium doped garnet, gadolinium-yttrium-scandium-gallium-aluminum garnet and crystal growth method by melt method
CN101671844A (en) * 2009-09-30 2010-03-17 中国科学院安徽光学精密机械研究所 Ca, Mg, Zr, Gd and Ga garnet doped with Sm and melt method crystal growth method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101476156A (en) * 2008-12-30 2009-07-08 中国科学院安徽光学精密机械研究所 Gadolinium, yttrium, scandium and gallium doped garnet, gadolinium-yttrium-scandium-gallium-aluminum garnet and crystal growth method by melt method
CN101671844A (en) * 2009-09-30 2010-03-17 中国科学院安徽光学精密机械研究所 Ca, Mg, Zr, Gd and Ga garnet doped with Sm and melt method crystal growth method thereof

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Application publication date: 20140813