CN103882523A - Chromium-doped aluminium borate scandium-lanthanum tunable laser crystal - Google Patents
Chromium-doped aluminium borate scandium-lanthanum tunable laser crystal Download PDFInfo
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- CN103882523A CN103882523A CN201410130090.6A CN201410130090A CN103882523A CN 103882523 A CN103882523 A CN 103882523A CN 201410130090 A CN201410130090 A CN 201410130090A CN 103882523 A CN103882523 A CN 103882523A
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Abstract
The invention discloses a chromium-doped aluminium borate scandium-lanthanum tunable laser crystal and a preparation method thereof. The molecular formula of the crystal is Cr<3+>:LaSc[3-x]Alx(BO3)4, wherein x ranges from 0.5 to 1.5, the doping concentration of Cr<3+> is 0.2-5 mol.%, and the crystal can grow by means of a pulling method and a top seed crystal molten-salt growth method. The crystal has the characteristics of being good in thermal and mechanical performances, large in absorption and emission sections, and the like, has a tunable range from 800 to 1050 nm, is expected to be a novel tunable laser crystal, and acquires actual applications.
Description
Technical field
The present invention relates to technical field of optoelectronic functional materials, particularly relate to a kind of laser crystal material as operation material in tunable solid laser apparatus.
Background technology
Tunable laser refers to: by the active ions in pump light excitation laser working medium, make to produce laser, this Laser emission peak is a ripple bag with wider wavelength region, or in a certain wavelength region, there are multiple emission peaks, adopt on this basis the method such as prism tuning method, F-P etalon tuning method, grating tuning method, color filter tuning method and distributed feed-back system tunning method to obtain wavelength adjustable Laser output within the specific limits.
Adopt flash lamp pumping from people such as L.F.Johnson in 1963, mixing Ni
2+mgF
2in crystal, realize first solid adjustable laser operation (L.F.Johnson, R.E.Dietz and H.J.Guggenheim, J.Phys.Rev.Lett., 11 (1963) 318) since, scientists has been found a lot of solid adjustable laser crystalss, as Ti
3+: Al
2o
3, Cr
3+: Mg
2siO
4, Cr
3+: LiSrAlF
6, Cr
3+: BeAl
2o
4deng, but due to a variety of causes, most of tunable laser crystals are only limited to laboratory and use, and cannot push industrial application to.At present most study, the solid adjustable laser crystals that enters Application Areas are Cr
3+: BeAl
2o
4(alexandrite crystal), Ti
3+: Al
2o
3(titanium-doped sapphire) and Cr
3+: LiCaAlF
6, Cr
3+: LiSrAlF
6, but the defect that they also all exist some to be difficult to avoid is restricted their range of application.As: Cr
3+: BeAl
2o
4the main drawback of (alexandrite crystal) crystal is: tuning range is less, and between 700～800nm, emission cross section is little by (6 × 10
-21cm
2), pumping threshold is high, has high damage rate and high thermal lensing effect etc., in addition due to BeO severe toxicity, also brings very large difficulty to growth.Ti
3+: Al
2o
3the main drawback of crystal is: Ti in this crystal
3+-Ti
4+the appearance of ion pair, make at Laser output wave band, be that absorbing appears in near-infrared band, affect its laser activity, and (only have 3.2 μ s) because its upper laser level life-span is short, need, with short-pulse laser, Q-switch laser, continuous wave laser or the flash lamp pumping that produces special short pulse, also further limit its application.Cr
3+: LiCaAlF
6, Cr
3+: LiSrAlF
6there is the problems such as uptake factor is little, the lasing efficiency of laser diode (LD) pumping is low in crystal.
The various composite factors of using from solid adjustable laser crystals consider also do not have a kind of crystal can meet well people's demand at present.Therefore, find tunable range wider, and can directly use the tunable laser crystal material of LD pumping to become one of focus of current laser crystals research field.
Summary of the invention
Object of the present invention is just to develop a kind of novel tunable laser crystal, and it can directly use LD pumping, has wider tunable range.
Boric acid scandium lanthanum (LaSc
3(BO
3)
4) be a kind of well laser host material, its quality is hard, has good heat conductivility, has good optical characteristics, and available crystal pulling method carries out crystal growth, Nd
3+: LaSc
3(BO
3)
4crystal is as the laser crystal material that is applicable to LD pumping, by people's report (J-P.Meyn such as German J-P.Meyn, T.Jensen, G.Huber, IEEE J.Quantum Electronics, 30 (1994): 913), its output wavelength is 1.06 μ m, has obtained good experimental result.But because its fusing point is higher than 1500 DEG C, B in crystal growing process
2o
3easily volatilization, causes component deviation stoichiometric ratio, causes crystal mass to have larger defect, affects its use; In addition in crystal composition, contain a large amount of Sc compositions, it is expensive, causes crystal cost high, has also affected its practical application.The chromium aluminum borate scandium lanthanum (Cr that mixes of the present invention
3+: LaSc
3-xal
x(BO
3)
4) crystal, adopt Al
3+substitute Sc
3+, due to Al
3+radius is less than Sc
3+, its alternative Sc
3+when crystallographic site, will cause structure compacter, compound is more stable, thereby suppresses LaSc
3-xal
x(BO
3)
4decomposition and B
2o
3volatilization, be conducive to crystal growth; In the periodic table of elements, because Al and Sc belong to congeners, there is similar character, therefore Al
3+substitute Sc
3+after, by not causing large impact to the various physical and chemical performances of matrix itself, can not affect the spectral response curve of dopant ion, Cr
3+after mixing, ion will still there is wide Absorption and emission spectra; Another Al
2o
3cheap, will significantly reduce crystal raw material cost.Experimental result shows to mix chromium aluminum borate scandium lanthanum (Cr
3+: LaSc
3-xal
x(BO
3)
4) crystal can be used as a kind of novel tunable laser crystal material.
Technical scheme of the present invention is as follows:
Concrete chemical equation:
yCr
2O
3+La
2O
3+(3-x-y)Sc
2O
3+xAl
2O
3+8H
3BO
3=2Cr
y:LaSc
3-x-yAl
x(BO
3)
4+12H
2O
(x=0.5-1.5,y=0.002-0.05)
3Li
2CO
3+4H
3BO
3=Li
6B
4O
9+6H
2O+3CO
2
Material purity used and producer:
| Medicine name | Purity | Producer |
| Cr 2O 3 | 99.9% | Solution on Chemical Reagents in Shanghai company of Chinese Medicine group |
| La 2O 3 | 99.99% | Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences |
| Sc 2O 3 | 99.99% | Changchun Applied Chemistry Research Inst., Chinese Academy of Sciences |
| Al 2O 3 | 99.95% | Solution on Chemical Reagents in Shanghai company of Chinese Medicine group |
| H 3BO 3 | 99.95% | Solution on Chemical Reagents in Shanghai company of Chinese Medicine group |
| Li 2CO 3 | 99.95% | Solution on Chemical Reagents in Shanghai company of Chinese Medicine group |
Mix chromium aluminum borate scandium lanthanum (Cr
3+: LaSc
3-xal
x(BO
3)
4) crystal is a kind of novel tunable laser crystal, can grow by crystal pulling method and top seed crystal molten-salt growth method.
Czochralski grown Cr
3+: LaSc
3-xal
x(BO
3)
4crystal, by the molecular formula of crystal sample, mixing, compressing tablet (wherein Cr
2o
3, Al
2o
3and Sc
2o
3add by desired concn), be grown in iraurite crucible and carry out, adopt rare gas element (as N
2, Ar etc.) protection, 1560 DEG C of growth temperatures, pulling speed is 0.5～2.0mm/h, crystal rotating speed is 5～20r/min, has grown high-quality being of a size of
20 × 25mm
3cr
3+: LaSc
3-xal
x(BO
3)
4crystal.(seeing embodiment 1)
With Li
2cO
3: H
3bO
3the synthetic compound L i of=3:4 (mol ratio)
6b
4o
9for fusing assistant, fusing assistant shared concentration ratio in growth raw material is 35～65wt.%, 1050～850 DEG C of growth temperatures, and rate of temperature fall is 0.5～2 DEG C/day, and crystal rotating speed is 5～30 revs/min, and growth cycle is 15～30 days.After one-period (15～30 days), obtain crystal boundary, good 30 × 25 × 20mm that is of a size of of optical homogeneity
3cr
3+: LaSc
3-xal
x(BO
3)
4crystal.(seeing embodiment 2)
By the Cr growing
0.0065: LaSc
1.9935al (BO
3)
4crystal carries out the measurement of absorption spectrum, fluorescence Spectra and fluorescence lifetime under room temperature.Can find out from its absorption spectrum: crystal has two wider absorption bands between 400～530nm and 560～750nm, and uptake factor is respectively 1.13cm
-1and 1.35cm
-1.From Cr
0.01: LaSc
1.99al (BO
3)
4in the room temperature fluorescence spectrum of crystal, visible this crystal has a wider emission peak between 780～1100nm, and emission peak is positioned at 910nm, and the full width at half maximum at peak is 205nm, and fluorescence lifetime is 37.7 μ s, can between 800～1050nm, carry out tuning.
The chromium aluminum borate scandium lanthanum (Cr that mixes of the present invention
3+: LaSc
3-xal
x(BO
3)
4) tunable laser crystal, can easily grow by crystal pulling method and molten-salt growth method, growth technique is simple, and raw material is easy to get, inexpensive.Crystal has the features such as good machinery and thermal property, tunable wide waveband, Absorber Bandwidth, is applicable to using the plurality of advantages such as LD pumping, and this crystal can be used as a kind of tunable laser crystal preferably.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but should not limit the scope of the invention with this.
Embodiment 1: Czochralski grown doping content is 1.0mol.%Cr
3+cr
0.01: LaSc
1.99al (BO
3)
4crystal
?
50 × 40mm
3iraurite crucible in, put into 200gCr synthetic, that press sheet
0.01: LaSc
1.99al (BO
3)
4raw material, after vacuumizing, is filled with N
2, adopt crystal pulling method, at 1560 DEG C, with the pulling speed of 1.0mm/h, the crystal rotating speed of 10rpm, grows and is of a size of
20 × 25mm
3cr
3+: LaSc
1.99al (BO
3)
4crystal.Show Cr in crystal through plasmatron spectrographic analysis
3+ion content is 0.65mol.%.
Embodiment 2: with Li
6b
4o
9for fusing assistant, adopting top seed crystal molten-salt growth doping content is 3.0mol.%Cr
3+cr
0.03: LaSc
1.47al
1.5(BO
3)
4crystal
Growth raw material is LaCr
0.03sc
1.47al
1.5(BO
3)
4: Li
6b
4o
9=0.45:0.55 (weight ratio).Accurately take raw material in above ratio, after being ground, being placed in and being of a size of
60 × 50mm
3platinum alloy crucible in, growth temperature is 1025 DEG C → 985 DEG C, with the rate of temperature fall of 2.0 DEG C/day, the crystal rotating speed of 20 revs/min, grew and has been of a size of 25 × 8 × 1mm through 20 days
3cr
3+: LaSc
1.47al
1.5(BO
3)
4crystal.Show Cr in crystal through plasmatron spectrographic analysis
3+ion content is 1.3mol.%.
Claims (3)
1. mix a chromium aluminum borate scandium lanthanum tunable laser crystal, it is characterized in that: the molecular formula of described crystal is Cr
3+: LaSc
3-xal
x(BO
3)
4, wherein the span of x is: 0.5-1.5, Cr
3+doping content be: 0.2-5mol.%, can produce tunable laser output.
2. a preparation method for laser crystals described in claim 1, adopts crystal pulling method, it is characterized in that: growth conditions is: adopt iraurite crucible, in rare gas element, carry out, 1560 DEG C of growth temperatures, pull rate is 0.5～2.0mm/h, crystal rotating speed is 5～20r/min.
3. a preparation method for laser crystals described in claim 1, adopts top seed crystal molten-salt growth method, it is characterized in that: with Li
6b
4o
9for fusing assistant, fusing assistant shared concentration ratio in growth raw material is 35～65wt.%, 1050～850 DEG C of growth temperatures, and rate of temperature fall is 0.5～2 DEG C/day, crystal rotating speed is 5～30r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410130090.6A CN103882523A (en) | 2014-04-01 | 2014-04-01 | Chromium-doped aluminium borate scandium-lanthanum tunable laser crystal |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410130090.6A CN103882523A (en) | 2014-04-01 | 2014-04-01 | Chromium-doped aluminium borate scandium-lanthanum tunable laser crystal |
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Family
ID=50951632
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| CN201410130090.6A Pending CN103882523A (en) | 2014-04-01 | 2014-04-01 | Chromium-doped aluminium borate scandium-lanthanum tunable laser crystal |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358537A (en) * | 2019-07-11 | 2019-10-22 | 东南大学 | A kind of garnet fluorescent powder and preparation method thereof for LED plant growth lamp |
| CN112342021A (en) * | 2019-08-07 | 2021-02-09 | 厦门稀土材料研究所 | Near-infrared broadband emission luminescent material, preparation method thereof and luminescent device comprising material |
| CN114959897A (en) * | 2022-04-25 | 2022-08-30 | 同济大学 | Chromium-doped lutetium scandium ultrafast ultrastrong laser crystal and preparation method and application thereof |
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Patent Citations (8)
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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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358537A (en) * | 2019-07-11 | 2019-10-22 | 东南大学 | A kind of garnet fluorescent powder and preparation method thereof for LED plant growth lamp |
| CN112342021A (en) * | 2019-08-07 | 2021-02-09 | 厦门稀土材料研究所 | Near-infrared broadband emission luminescent material, preparation method thereof and luminescent device comprising material |
| CN114959897A (en) * | 2022-04-25 | 2022-08-30 | 同济大学 | Chromium-doped lutetium scandium ultrafast ultrastrong laser crystal and preparation method and application thereof |
| CN114959897B (en) * | 2022-04-25 | 2024-03-26 | 同济大学 | Chromium-doped lutetium scandium ultra-fast ultra-strong laser crystal and preparation method and application thereof |
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