CN112952544B - Dysprosium terbium aluminum tri-doped yellow laser crystal and preparation method and application thereof - Google Patents
Dysprosium terbium aluminum tri-doped yellow laser crystal and preparation method and application thereof Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 104
- -1 Dysprosium terbium aluminum Chemical compound 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 230000003595 spectral effect Effects 0.000 claims abstract description 6
- 230000003287 optical effect Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 13
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 10
- 229910052771 Terbium Inorganic materials 0.000 claims description 10
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 230000009849 deactivation Effects 0.000 claims description 3
- ARWMTMANOCYRLU-UHFFFAOYSA-N [Ca].[La] Chemical compound [Ca].[La] ARWMTMANOCYRLU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001719 melilite Inorganic materials 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
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- 230000007704 transition Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 229910052741 iridium Inorganic materials 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001195 gallium oxide Inorganic materials 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 239000002178 crystalline material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/1601—Solid materials characterised by an active (lasing) ion
- H01S3/1603—Solid materials characterised by an active (lasing) ion rare earth
- H01S3/1606—Solid materials characterised by an active (lasing) ion rare earth dysprosium
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- H—ELECTRICITY
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- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/163—Solid materials characterised by a crystal matrix
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/1691—Solid materials characterised by additives / sensitisers / promoters as further dopants
- H01S3/1693—Solid materials characterised by additives / sensitisers / promoters as further dopants aluminium
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- H—ELECTRICITY
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- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
- H01S3/14—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range characterised by the material used as the active medium
- H01S3/16—Solid materials
- H01S3/1691—Solid materials characterised by additives / sensitisers / promoters as further dopants
- H01S3/1698—Solid materials characterised by additives / sensitisers / promoters as further dopants rare earth
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The application discloses a novel dysprosium terbium aluminum triple-doped yellow laser crystal and a preparation method and application thereof, relating to the field of laser crystal materials and having a specific chemical formula of CaDy x Tb y La (1‑x‑y) Al z Ga 3‑z O 7 Wherein, 0<x≤0.05，0<y≤0.01，0<z is less than or equal to 0.6; in the crystal material, Dy 3+ The ions are used as active ions to realize yellow light emission in the 560-600nm wave band, and the corresponding energy level transition is Dy 3+ : 4 F 9/2 → 6 H 13/2 ；Tb 3+ As a deactivating ion to accelerate Dy 3+ Laser lower energy level 6 H 13/2 The relaxation speed of the laser is reduced, so that the radiation life of the lower energy level of the laser is effectively shortened, and the rapid inverse distribution of the particle number is realized; al (aluminum) 3+ The ion as non-optical active ion is favorable for forming local disordered structure of mixed crystal, causing the disordered degree of the crystal to be increased and regulating Dy 3+ The multiple luminous centers play a role in widening luminous spectral lines. Dy is realized based on the novel dysprosium terbium aluminum triple-doped crystal 3+ And outputting all solid-state yellow laser of the ions.
Description
Technical Field
The invention relates to the field of inorganic crystal materials, in particular to a dysprosium terbium aluminum triple-doped yellow laser crystal and a preparation method and application thereof.
Background
The yellow laser (wavelength range 560-. At present, laser output of visible light bands such as red, green and blue can be obtained by a nonlinear frequency conversion technology, and the conversion efficiency is high, however, yellow laser cannot be directly realized by a Laser Diode (LD) pumping technology due to the lack of corresponding fundamental frequency light. Therefore, yellow lasers have been developing very slowly over the past few decades. In recent years, due to the great push of the LED illumination revolution, InGaN/GaN-based blue laser diodes have developed greatly, which provides a new feasible way for the blue LD to directly pump the crystal activated by rare earth ions to generate yellow laser in a one-step manner, thereby initiating a new research trend in the scientific and technological field and leading the research of the yellow laser to enter a new stage.
Research has found that in recent years, there is no new major breakthrough neither domestically nor abroad, and crystals that have achieved yellow laser output at present are mainly focused on fluorides, YAG, and tungstates. For fluoride, the phonon energy is low, which is not beneficial to the population inversion between the upper energy level and the lower energy level of laser, so that the laser power is difficult to be greatly improved; YAG as yellow laser gain medium has certain limitation, and its upper energy level increases with the doping concentration of Dy 4 F 9/2 Fast reduction of lifetime, and lower energy level 6 H 13/2 Quenching rapidly due to electron-phonon coupling, Dy 3+ The lower energy level lifetime is only 10 μ s at a doping concentration of 3 at.%, which is extremely disadvantageous for realizing a yellow laser output; and the tungstate is used as a yellow laser gain medium, and the output efficiency is difficult to be greatly improved due to poor thermal conductivity.
Based on the analysis, the project aims to protect a novel dysprosium terbium aluminum triple-doped yellow laser crystal material. According to research, 570-doped 600 nm-waveband dysprosium terbium aluminum triple-doped yellow laser crystal is not reported at home and abroad at present.
Disclosure of Invention
The invention aims to provide a dysprosium terbium aluminum triple-doped yellow laser crystal and a preparation method and application thereof. The laser crystal can achieve the effect of emitting 560-600nm high-efficiency yellow laser.
In order to achieve the effect, the invention discloses a dysprosium terbium aluminum triple-doped yellow laser crystal which realizes the output of 560-terbium-aluminum-doped 600nm high-efficiency yellow laser based on the co-doping of dysprosium, terbium and aluminum with lanthanum calcium gallate, wherein dysprosium is used as an activating ion, terbium is used as a deactivating ion, aluminum is used as a non-optically active ion, the disorder degree of the crystal is increased, and the emission spectral line is widened. In the laser crystal, Dy 3+ The ions are used as activating ions to realize 560-600nm yellow light emission, and the corresponding energy level transition is Dy 3 + : 4 F 9/2 → 6 H 13/2 ；Tb 3+ Ions as deactivating ions to accelerate Dy 3+ Laser lower energy level 6 H 13/2 The relaxation speed of the laser is reduced, so that the radiation life of the lower energy level of the laser is effectively shortened, and the rapid inverse distribution of the particle number is realized; al (Al) 3+ The ion as the non-optically active ion has the following specific actions: is favorable for forming a local disordered structure of mixed crystals, causes the disordered degree of the crystals to be increased, and regulates and controls Dy 3+ The multiple luminous centers can play a role in broadening luminous spectral lines, so that broadband yellow light emission with specific wavelength required by people is obtained; the consumption of gallium oxide can be reduced, so that the volatilization of gallium oxide in the crystal growth process is reduced, and the problem of serious volatilization of gallium oxide is radically solved, thereby achieving the purpose of improving the crystal quality; ③ lower cost because of Ga 2 O 3 The price of the alloy is much higher than that of Al 2 O 3 。
Further, the chemical formula of the laser crystal is:
CaDy x Tb y La (1-x-y) Al z Ga 3-z O 7
wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.01, and z is more than 0 and less than or equal to 0.6;
dy in the crystal material 3+ And Tb 3+ Substitution of Ca in the crystals 2+ /La 3+ Lattice site of (C), Al 3+ By substitution of Ga in the crystal 3+ Lattice site of (2), Ca 2+ 、Dy 3+ 、Tb 3+ And La 3+ Randomly distributed in GaO 4 /AlO 4 The tetrahedron forms a layered electronegative skeleton structure, and has a disordered melilite structure.
Further, the laser crystal contains a broadband emission peak between 560-600nm in the yellow light band.
The invention also discloses a preparation method of the dysprosium terbium aluminum tri-doped yellow laser crystal, which at least comprises the following steps:
the polycrystal of the crystal material is prepared by the raw materials containing the calcium source, the lanthanum source, the terbium source, the gallium source, the aluminum source and the dysprosium source through a high-temperature solid phase method.
Further, the method also comprises the following steps: and growing the polycrystal obtained by the steps by adopting a melt pulling method to obtain a monocrystal of the crystal material.
Further, the calcium source is CaCO with a purity of 99.98% 3 (ii) a The lanthanum source is La of 4N grade 2 O 3 (ii) a The terbium source is Tb of 4N grade 2 O 3 (ii) a The gallium source is Ga of 4N grade 2 O 3 (ii) a The aluminum source is 4N-grade Al 2 O 3 (ii) a The dysprosium source is Dy of 4N grade 2 O 3 ；
The raw materials contain calcium element, dysprosium element, terbium element, lanthanum element, aluminum element and gallium element in a molar ratio of
Ca：Dy：Tb：La：Al：Ga= 1：x：y：(1-x-y)：z：3-z；
Wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.01, and z is more than 0 and less than or equal to 0.6.
Preferably, the high temperature solid phase process comprises the steps of:
s1: pressing the raw materials into sheets, putting the sheets into a corundum crucible, putting the corundum crucible into a high-temperature sintering furnace, slowly heating to 1000-1100 ℃ at a heating rate of not more than 200 ℃/h, keeping the temperature for not less than 6 h, then heating to 1200-1300 ℃, sintering at constant temperature for 48-96 h, and taking out a sample;
s2: repeat step S1: until the X-ray powder diffraction of the sample completely conformed to the standard card.
Preferably, the melt-pulling method is as followscCaLaGa in axial direction 3 O 7 The substrate crystal is used as a seed crystal, the pulling rate of a seed crystal rod is 0.7-5.0 mm/h, the cooling rate is 1-10 ℃/h, and the rotation rate of the seed crystal rod is 2-10 r.p.m.; and after the growth is finished, lifting the crystal away from the liquid level, keeping the temperature of 3-30 ℃ and slowly cooling to room temperature to prevent the crystal from cracking in the cooling process, and thus obtaining the monocrystal of the crystal material.
As a specific embodiment, the melt pulling method comprises the steps of:
putting the polycrystal into an iridium crucible and placing the crucible into a crystal pulling furnace; and vacuumizing the crystal pulling furnace, filling protective gas, heating to a temperature which is 30-50 ℃ higher than the melting point, and keeping the temperature for half an hour to completely melt the raw materials. To be provided withcTangential CaLaGa 3 O 7 The crystal is used as a seed crystal, the pulling rate of a seed crystal rod in the growth process is 0.7-5.0 mm/h, and the cooling rate is 1-10 0 C/h, the rotation rate of the seed rod is 2-10 r.p.m; and after the growth is finished, lifting the crystal away from the liquid level, keeping the temperature of 3-30 ℃ and slowly cooling to room temperature to prevent the crystal from cracking in the cooling process, and obtaining the transparent single crystal with the size of phi 20 mm multiplied by 40 mm.
Preferably, the resulting single crystal has at least one dimension in excess of 10 mm; preferably, the resulting single crystal has at least one dimension in excess of 20 mm.
The invention also discloses application of the dysprosium terbium aluminum tri-doped yellow laser crystal, which is used for realizing 560-doped 600nm all-solid-state yellow laser output. Can be widely applied to the fields of biological military, laser radar, scientific research and the like.
The invention has the beneficial effects that:
(1) tb in the dysprosium terbium aluminum tri-doped novel yellow laser crystal 3+ Effective doping of ions to accelerate Dy 3+ Laser lower energy level 6 H 13/2 The relaxation speed of the laser is reduced, so that the radiation life of the lower energy level of the laser is effectively shortened, and the rapid inverse distribution of the particle number is realized; non-optically active ionic Al 3+ The doping of (2) greatly increases the disorder degree of the crystal, widens the yellow light emission spectral line, and is beneficial to realizing Dy 3+ High-efficiency yellow laser output of ions.
(2) The invention successfully grows the dysprosium terbium aluminum tri-doped novel yellow laser crystal for the first time internationally, the optical performance of the 560 + 600nm waveband is studied for the first time, and data shows that the crystal material can be used as a novel laser crystal material for realizing the output of 560 + 600nm yellow laser.
Drawings
FIG. 1 is a schematic diagram of the deactivation mechanism of a novel dysprosium terbium aluminum triple doped yellow laser crystal;
FIG. 2 is a powder diffraction pattern of the novel dysprosium terbium aluminum triple doped yellow laser crystal;
FIG. 3 is the fluorescence spectrum of the novel yellow laser crystal doped with dysprosium, terbium and aluminum.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, all materials and reagents used in the present application were purchased commercially and used as received without treatment, and the equipment used was the manufacturer's recommended protocol and parameters.
In the embodiment, the apparatus used for the crystal pulling method is a 50 pulling furnace produced by the twenty-sixth group of electronic technology in China; the protective atmosphere is 98 percent N 2 +2% O 2 (ii) a The crucible used was an iridium crucible of phi 62 mm x 40 mm.
In the examples, the starting material used was CaCO having a purity of 99.98% 3 La of grade 4N 2 O 3 Class 4N Tb 2 O 3 Grade 4N Al 2 O 3 Ga of 4N grade 2 O 3 And Dy of 4N class 2 O 3 。
In the examples, the powder diffractogram of the crystal sample was measured on an X-ray diffractometer Miniffex-600 manufactured by Japan Physics; the fluorescence spectrum of the yellow band was measured on a FLS980 fluorescence spectrometer, produced by Edinburgh, UK.
Preparation of a sample of crystalline Material
Weighing CaCO according to the proportion in the following chemical reaction formula 3 、Tb 2 O 3 、La 2 O 3 、Al 2 O 3 、Ga 2 O 3 And Dy 2 O 3 And uniformly mixing to obtain the following raw materials:
2CaCO 3 +(1-x-y)La 2 O 3 +yTb 2 O 3 +xDy 2 O 3 +(3-z)Ga 2 O 3 +zAl 2 O 3 →2 CaDy x Tb y La (1-x-y) Al z Ga 3-z O 7 +2CO 2 ↑
pressing the raw materials into sheets, putting the sheets into a corundum crucible, putting the corundum crucible into a high-temperature sintering furnace, slowly heating the corundum crucible to 1000-1100 ℃ at a certain speed, and keeping the corundum crucible for a period of time; then heating to a sintering temperature and sintering at a constant temperature for a period of time, and taking out a sample; repeating the sintering step until the powder diffraction of X-ray and CaLaGa 3 O 7 Until the XRD standard JCPDS cards of the crystals completely conform to each other, a polycrystal sample of the crystal material is obtained.
The raw materials are filled into an iridium crucible with the diameter of 62 mm multiplied by 40 mm, in order to avoid the oxidation of the iridium crucible, air in a furnace is firstly pumped out, the air pressure in the furnace is about-0.01 Mpa, then protective gas is filled in to ensure that the air pressure reaches 0.12 Mpa, then the temperature is raised to the temperature which is 30-50 ℃ higher than the melting point, and the constant temperature is kept for half an hour to ensure that the raw materials are completely melted. To be provided withcTangential CaLaGa 3 O 7 The crystal is used as a seed crystal, the pulling rate of a seed rod in the growth process is a certain value within the range of 0.7-5.0 mm/h, the cooling rate is a certain value within the range of 1-10 ℃/h, the rotation rate of the seed rod is a certain value within the range of 2-10 r.p.m., the crystal is lifted from the liquid level after the growth is finished, and in order to prevent the crystal from cracking in the cooling process, the crystal is slowly cooled to room temperature at the rate of 3-30 ℃, so that a transparent single crystal sample of the crystal material is obtained. The deactivation mechanism of the dysprosium terbium aluminum tri-doped yellow laser crystal is shown in figure 1, and the powder diffraction pattern of the obtained crystal sample is shown in figure 2.
The relationship between the serial number of the obtained sample and the values x, y and z in the chemical formula, the sintering condition in the high-temperature sintering process, the pulling rate and the cooling rate of the seed rod in the crystal growing process by the pulling method, the rotation rate of the seed rod, the cooling rate of the temperature of the seed rod leaving the liquid level after the growth and reducing to the room temperature, and the size of the obtained sample is shown in table 1.
TABLE 1
Second, optical property measurement of the obtained sample
Samples were taken separately S1 # ~S3 # And machining to obtain a workpiece with a dimension of 3.0X 5.0X (0.8-1.3) mm 3 The crystal sheet of (4) was subjected to a spectroscopic property test study.
The results show that sample S1 # ~S3 # A wide fluorescence emission peak corresponding to Dy is arranged between 560-doped 600nm 3+ : 4 F 9/2 → 6 H 13/2 The transition is very favorable for realizing the output of 560-600nm yellow laser.
As sample S1 # As a representative example, the powder diffraction pattern and the fluorescence spectrum of the yellow band of the sample are shown in FIG. 2 and FIG. 3, respectively. Sample S2 # And S3 # The fluorescence spectrum of the yellow band of (1) is similar to that of (3), except that the peak wavelengths of the respective peaks are slightly changed within a range of. + -. 5 nm depending on the values of x, y and z.
In conclusion, the invention utilizes the pulling method to grow the novel dysprosium terbium aluminum triple-doped yellow laser crystal in which Dy 3+ The ion is used as an activating ion to realize 560-doped 600nm broadband fluorescence output, and the energy level transition corresponding to luminescence is Dy 3+ : 4 F 9/2 → 6 H 13/2 ；Tb 3+ As deactivating ions to accelerate Dy 3+ Laser lower energy level 6 H 13/2 The relaxation speed of the laser is reduced, so that the radiation life of the lower energy level of the laser is effectively shortened, and the rapid inverse distribution of the particle number is realized; al (Al) 3+ The ion as non-optical active ion is favorable for forming local disordered structure of mixed crystal, causing the increase of disordered degree of crystal and regulating Dy 3+ Multiple luminescent centers, can broaden luminescent spectral lines, and is favorable for realizing Dy 3+ And outputting yellow laser of the ions. The dysprosium terbium aluminum triple-doped novel yellow laser crystal can be used for high-efficiency yellow laser output of 560-doped 600nm, and has wide application prospects in the fields of biomedical treatment, laser radar, scientific research and the like.
The above-mentioned embodiments are only preferred examples of the present invention, and should not be construed as limiting the scope of the invention, so that the equivalent changes or modifications made by the constructions, features and principles described in the claims of the present invention should be included in the scope of the present invention.
Claims (8)
1. A dysprosium terbium aluminum triple-doped yellow laser crystal is characterized in that: dysprosium in the crystal material is used as an active ion, terbium in the crystal material is used as a deactivation ion, and aluminum in the crystal material is used as a non-optical active ion, so that the disorder degree of the crystal is increased, and an emission spectral line is widened; based on three ions of dysprosium, terbium and aluminum co-doped lanthanum calcium gallate, 560-doped 600nm all-solid-state yellow laser output is realized;
the chemical formula of the laser crystal is as follows:
CaDy x Tb y La (1-x-y) Al z Ga 3-z O 7
wherein x is more than 0 and less than or equal to 0.05, y is more than 0 and less than or equal to 0.01, and z is more than 0 and less than or equal to 0.6;
dy in the crystal material 3+ And Tb 3+ Substitution of Ca in the crystals 2+ /La 3+ Lattice site of (1), Al 3+ By substitution of Ga in the crystal 3+ Lattice site of (C), Ca 2 + 、Dy 3+ 、Tb 3+ And La 3+ Randomly distributed in GaO 4 /AlO 4 The tetrahedron forms a layered electronegative skeleton structure and has a disordered melilite structure;
the laser crystal contains a broadband emission peak between 560-600nm in the yellow light band.
2. The method for preparing the dysprosium terbium aluminum tri-doped yellow laser crystal as claimed in claim 1, characterized by comprising at least the following steps:
the polycrystal of the crystal material is prepared by the raw materials containing the calcium source, the lanthanum source, the terbium source, the gallium source, the aluminum source and the dysprosium source through a high-temperature solid phase method.
3. The method for preparing a dysprosium terbium aluminum tri-doped yellow laser crystal according to claim 2, further comprising the steps of: and growing the polycrystal obtained by the steps by adopting a melt pulling method to obtain a monocrystal of the crystal material.
4. The method for preparing a dysprosium terbium aluminum tri-doped yellow laser crystal according to any one of claims 2 or 3, wherein the method comprises the following steps:
the calcium source is CaCO with a purity of 99.98% 3 (ii) a The lanthanum source is La of 4N grade 2 O 3 (ii) a The terbium source is Tb of 4N grade 2 O 3 (ii) a The gallium source is Ga of 4N grade 2 O 3 (ii) a The aluminum source is 4N-grade Al 2 O 3 (ii) a The dysprosium source is Dy of 4N grade 2 O 3 。
5. The method for preparing a dysprosium terbium aluminum tri-doped yellow laser crystal according to claim 3, wherein the method comprises the following steps: the melt pulling method is as followscCaLaGa in axial direction 3 O 7 The substrate crystal is used as a seed crystal, the pulling rate of a seed crystal rod is 0.7-5.0 mm/h, the cooling rate is 1-10 ℃/h, and the rotation rate of the seed crystal rod is 2-10 r.p.m.; and after the growth is finished, lifting the crystal away from the liquid level, keeping the temperature of 3-30 ℃ and slowly cooling to room temperature to prevent the crystal from cracking in the cooling process, and thus obtaining the monocrystal of the crystal material.
6. The method for preparing a dysprosium terbium aluminum tri-doped yellow laser crystal according to claim 5, wherein the method comprises the following steps: the resulting single crystal has at least one dimension in excess of 10 mm.
7. The method for preparing a dysprosium terbium aluminum tri-doped yellow laser crystal according to claim 6, wherein the method comprises the following steps: the resulting single crystal has at least one dimension in excess of 20 mm.
8. The application of the dysprosium terbium aluminum tri-doped yellow laser crystal as claimed in claim 1, which is used for realizing 560-600nm all-solid-state yellow laser output.
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| CN111575793A (en) * | 2020-05-29 | 2020-08-25 | 马鞍山市华宇环保设备制造有限公司 | Yb-doped gadolinium lanthanum silicate femtosecond laser crystal with ultra-wide emission spectral bandwidth |
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| CN107841789A (en) * | 2017-09-19 | 2018-03-27 | 同济大学 | Yttrium aluminate visible waveband laser crystal that a kind of dysprosium terbium is co-doped with and preparation method thereof |
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| CN111575793A (en) * | 2020-05-29 | 2020-08-25 | 马鞍山市华宇环保设备制造有限公司 | Yb-doped gadolinium lanthanum silicate femtosecond laser crystal with ultra-wide emission spectral bandwidth |
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