CN101378173B - Chromium-doped molybdic acid aluminum rubidium tunable laser crystal, and preparation method and application thereof - Google Patents
Chromium-doped molybdic acid aluminum rubidium tunable laser crystal, and preparation method and application thereof Download PDFInfo
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- CN101378173B CN101378173B CN2007100094367A CN200710009436A CN101378173B CN 101378173 B CN101378173 B CN 101378173B CN 2007100094367 A CN2007100094367 A CN 2007100094367A CN 200710009436 A CN200710009436 A CN 200710009436A CN 101378173 B CN101378173 B CN 101378173B
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Abstract
The invention discloses a tunable laser crystal doped with chrome, molybdenum, acid, aluminium and rubidium, and a preparation method and application thereof, and relates to a laser crystal material which can be used as the working substance of a tunable solid laser; the method adopts 60 to 80at percent of Rb2Mo3O10 as fusing assistant, with the temperature reduction speed of 1 to 5 DEG C/day and the rotating speed of 5 to 30 revolutions/minute, and Cr<3+>:RbAl(MoO4)2 crystal with high quality and larger size grows; and the crystal belongs to the trigonal system and has P3ml(D3d<3>) space group structure and the refractive index of 1.73. The crystal can be used as the tunable laser crystal with the tunable range between 710 to 1000nm and the solid laser made by the crystal can be used in the fields of spectroscopy, biomedicine and military science and the like.
Description
Technical field
The invention belongs to technical field of optoelectronic functional materials.Especially relate to a kind of laser crystal material as the operation material in the tunable solid laser.
Background technology
So-called tunable laser is meant a kind of like this effect: excited the active ions that mix in the solid matrix by laser or pumping lamp; To produce laser output, adopt methods such as prism tuning method, F-P etalon tuning method, grating tuning method, color filter tuning method and distributed feed-back system tuning method can obtain tunable laser output.
People such as L.F.Johnson adopted flash lamp pumping in 1963, were mixing Ni
2+MgF
2Realized first solid adjustable laser operation (L.F.Johnson R.E.Dietz&H.J.Guggenheim, J.Phys.Rev.Lett., 11 (1963) 318) in the crystal.A lot of tunable laser crystals have appearred subsequently, like Ti
3+: Al
2O
3, Cr
3+: Mg
2SiO
4, Cr
3+: LiSrAlF
6, Cr
3+: BeAl
2O
4Deng, but because a variety of causes, many tunable laser crystals are only limited to makes laboratory tool, can't push commercial Application to.The tunable laser crystal maximum, that got into application of research at present is Cr
3+: BeAl
2O
4(alexandrite crystal), Ti
3+: Al
2O
3(titanium-doped sapphire) and Cr
3+: Li CaAlF
6, Cr
3+: LiSrAlF
6, but the defective that they also all exist some to be difficult to avoid makes their range of application be restricted.
Cr
3+: BeAl
2O
4The major defect of (alexandrite crystal) crystal is: tuning range is between 700～800nm, and emission cross section is little by (6 * 10
-21Cm
2), required pumping threshold is high, but also has shortcomings such as high damage ratio and high thermal lensing effect, in addition because the BeO severe toxicity also brings very big difficulty to growth.
Ti
3+: Al
2O
3The major defect 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 near infrared band, influenced its laser activity, and because its upper laser level life-span short (having only 3.2 μ s); Need also further limit its application with short-pulse laser, Q switching laser, continuous wave laser or the flash lamp pumping that produces special short pulse.
Cr
3+: LiCaAlF
6, Cr
3+: LiSrAlF
6Plurality of advantages such as although crystal has the tuning range broad, emission cross section is big, and required pumping threshold is low.But also exist problems such as absorption coefficient is little, the lasing efficiency of LD pumping is low.All actively seeking the tunable laser crystal material that tuning band is wideer, can directly use photoflash lamp and LD pumping both at home and abroad at present.
Summary of the invention
The object of the invention just is to develop a kind of new tunable laser crystal, can directly use photoflash lamp and the tunable laser crystal material LD pumping, broad tuning.
RbAl (MoO
4)
2Belong to trigonal system, have P3ml (D
3d 3) the space group structure, be a kind of good laser crystal host material, chromium ion is can replace aluminum ions lattice position easily as dopant ion.Its doping content is between 0.2at%～5at%.Fluorescence lifetime (τ) is 17～30 μ s, and its fluorescence lifetime is the function of chromium ion concentration, can mix the chromium ion of variable concentrations according to different needs.Experimental result shows that its tunable range between 710～1000nm, can be used as tunable laser crystal.
Chromium-doped molybdic acid aluminum rubidium laser crystal and preparation method thereof: we have found growth Cr through experiment
3+: RbAl (MoO
4)
2The comparatively ideal flux of crystal: Rb
2Mo
3O
10, and best growth conditions, and grown high-quality crystal Cr
3+: RbAl (MoO
4)
2(seeing embodiment 1 and 2).
Concrete chemical equation is following:
Rb
2CO
3+Al
2O
3+4MoO
3＝2RbAl(MoO
4)
2+CO
2
Rb
2CO
3+3MoO
3＝Rb
2Mo
3O
10+CO
2
Used material purity and producer are following:
| The medicine name | Purity | Producer |
| Al 2O 3 | 99.999％ | Shanghai chemical reagents corporation of Chinese Medicine group |
| Cr 2O 3 | 99.95％ | Shanghai chemical reagents corporation of Chinese Medicine group |
| Rb 2CO 3 | 99.9％ | Jiangxi Gan Feng lithium industry Co., Ltd |
| MoO 3 | 99.99％ | Shanghai chemical reagents corporation of Chinese Medicine group |
Case of flux methods growth chromium-doped molybdic acid aluminum rubidium laser crystal, its main growth conditions is following: used flux is Rb
2Mo
3O
10, the total concentration of flux is controlled between 60～80at%, and growth temperature is between 650～570 ℃, and rate of temperature fall is 1～5 ℃/day, and the crystal rotating speed is 5～30rpm.
With the Cr that grows
3+: RbAl (MoO
4)
2Crystal has carried out the collection of diffraction data on four-circle diffractometer, structural analysis shows that it belongs to trigonal system, a=5.542
, c=7.490
, V=199.22 (6)
3, D
c=3.60g/cm
3Adopting immersion method to record its refractive index is 1.73.
With the Cr that grows
3+: RbAl (MoO
4)
2Crystal carries out the analytical test of absorption spectrum, fluorescence spectrum and fluorescence lifetime etc.From Cr
3+: RbAl (MoO
4)
2Absorption spectrum under the room temperature of crystal; It is thus clear that two strong absorption bands are arranged between 400～570nm and 580～800nm; Its peak value is respectively 478nm and 668nm, and two absorption bandwidth all are about 150nm, and can conveniently carry out pumping with photoflash lamp and LD; The absworption peak of broad helps the absorption of crystal to pump light, has improved power output.
From Cr
3+: RbAl (MoO
4)
2Fluorescence spectrum under the room temperature of crystal, visible have very strong fluorescent emission at 820nm, and its peak width is 700～1100nm, and its half-peak breadth is about 135nm, and emission cross section is 3.0 * 10
-20Cm
2, fluorescence lifetime is 25.7 μ s.Can between 710～1000 millimicrons, carry out tuning.
Visible from the above; Chromium-doped molybdic acid aluminum rubidium tunable laser crystal of the present invention has and can enough molten salt growth methods grow superior in quality crystal easily, and growth technique is stable; Has good heat-conducting; Good optical characteristics is arranged, and raw material is easy to get, the tunable laser wide waveband, can directly use plurality of advantages such as photoflash lamp and LD pumping, and this crystal can be used as a kind of laser crystal preferably.
Embodiment
Embodiment 1: with Rb
2Mo
3O
10For fluxing agent growth grow doping concentration is 1.0at.%Cr
3+Cr
3+: RbAl (MoO
4)
2Laser crystal.
Growth raw material is RbAl (MoO
4)
2: Rb
2Mo
3O
10=1: 2 (mol ratios) are mixed the Cr of 1.0at%
3+Ion.Adopt the fused salt top-seeded solution growth, in φ 60 * 50mm platinum alloy crucible, growth temperature is between 650 → 570 ℃, and with 2 ℃/day rate of temperature fall, 15 rev/mins crystal rotating speed has grown and has been of a size of 30 * 20 * 13mm
3High-quality Cr
3+: RbAl (MoO
4)
2Crystal.Show Cr in the crystal through ICP (plasma emission spectrum) analysis
3+Ion concentration is 1.0at%.。
Embodiment 2: with Rb
2Mo
3O
10For fluxing agent growth grow doping concentration is 2.0at.%Cr
3+Cr
3+: RbAl (MoO
4)
2Laser crystal.
Growth raw material is RbAl (MoO
4)
2: Rb
2Mo
3O
10=1: 2.0 (mol ratios) are mixed the Cr of 2.0at%
3+Ion.Adopt the fused salt top-seeded solution growth, in φ 60 * 50mm platinum alloy crucible, growth temperature is between 645 → 580 ℃, and with 3 ℃/day rate of temperature fall, 20 rev/mins crystal rotating speed has grown and has been of a size of 30 * 15 * 16mm
3High-quality Cr
3+: RbAl (MoO
4)
2Crystal.Show Cr in the crystal through ICP (plasma emission spectrum) analysis
3+Ion concentration is 2.0at%.
Claims (6)
1. chromium-doped molybdic acid aluminum rubidium tunable laser crystal, it is characterized in that: the molecular formula of this crystal is Cr
3+: RbAl (MoO
4)
2, belong to trigonal system, have
(D
3d 3) the space group structure, cell parameter does
D
c=3.60g/cm
3, can produce tunable laser.
2. chromium-doped molybdic acid aluminum rubidium tunable laser crystal as claimed in claim 1 is characterized in that: chromium ion is as dopant ion, and its valence state is+3 valencys, replaces aluminum ions lattice position, and its doping content is between 0.2at%～5at%.
3. the preparation method of the described chromium-doped molybdic acid aluminum rubidium tunable laser crystal of claim 1 is characterized in that: this crystal by adopting fused salt top-seeded solution growth growth, used flux is Rb
2Mo
3O
10, concentration is controlled between 20at～40at%, and growth temperature is between 660～560 ℃, and rate of temperature fall is 1～5 ℃/day, and the crystal rotating speed is 5～30rpm.
4. the purposes of a chromium-doped molybdic acid aluminum rubidium tunable laser crystal as claimed in claim 1; It is characterized in that: this crystal is used for tunable solid laser as operation material; Can obtain the laser output of broad tuning, its tunable range is between 710～1000nm.
5. the purposes of chromium-doped molybdic acid aluminum rubidium tunable laser crystal as claimed in claim 1 is characterized in that: this crystal uses photoflash lamp or laser diode as pumping source, excites to produce tunable laser output.
6. like the purposes of claim 1 or 5 described chromium-doped molybdic acid aluminum rubidium tunable laser crystals, it is characterized in that: the solid state laser of processing with this crystal is used for spectroscopy, biomedicine, military field.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100094367A CN101378173B (en) | 2007-08-30 | 2007-08-30 | Chromium-doped molybdic acid aluminum rubidium tunable laser crystal, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100094367A CN101378173B (en) | 2007-08-30 | 2007-08-30 | Chromium-doped molybdic acid aluminum rubidium tunable laser crystal, and preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101378173A CN101378173A (en) | 2009-03-04 |
| CN101378173B true CN101378173B (en) | 2012-07-18 |
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|---|---|---|---|
| CN2007100094367A Expired - Fee Related CN101378173B (en) | 2007-08-30 | 2007-08-30 | Chromium-doped molybdic acid aluminum rubidium tunable laser crystal, and preparation method and application thereof |
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| CN116925759A (en) * | 2023-07-25 | 2023-10-24 | 昆明理工大学 | Chromium-activated broadband near-infrared oxide fluorescent powder and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621579A (en) * | 2003-11-27 | 2005-06-01 | 中国科学院福建物质结构研究所 | Self frequency-conversion laser crystal rare earth ion activated rare earth molybdenate |
| CN1837421A (en) * | 2005-03-25 | 2006-09-27 | 中国科学院福建物质结构研究所 | Neodymium doped LiGd(MoO4)2 laser crystal, its preparation method and use |
| CN1848562A (en) * | 2005-04-05 | 2006-10-18 | 中国科学院福建物质结构研究所 | Laser crystal doping neodymium lanthanum potassium molybdate |
| CN1966780A (en) * | 2005-11-14 | 2007-05-23 | 中国科学院福建物质结构研究所 | Neodymium-doped sodium-yttrium molybdenate laser crystal and its preparation method and use |
-
2007
- 2007-08-30 CN CN2007100094367A patent/CN101378173B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621579A (en) * | 2003-11-27 | 2005-06-01 | 中国科学院福建物质结构研究所 | Self frequency-conversion laser crystal rare earth ion activated rare earth molybdenate |
| CN1837421A (en) * | 2005-03-25 | 2006-09-27 | 中国科学院福建物质结构研究所 | Neodymium doped LiGd(MoO4)2 laser crystal, its preparation method and use |
| CN1848562A (en) * | 2005-04-05 | 2006-10-18 | 中国科学院福建物质结构研究所 | Laser crystal doping neodymium lanthanum potassium molybdate |
| CN1966780A (en) * | 2005-11-14 | 2007-05-23 | 中国科学院福建物质结构研究所 | Neodymium-doped sodium-yttrium molybdenate laser crystal and its preparation method and use |
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