CN105887200A - Thulium-holmium-codoped strontium lanthanum gallate laser crystal, preparation method and application of crystal - Google Patents

Thulium-holmium-codoped strontium lanthanum gallate laser crystal, preparation method and application of crystal Download PDF

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CN105887200A
CN105887200A CN201610379258.6A CN201610379258A CN105887200A CN 105887200 A CN105887200 A CN 105887200A CN 201610379258 A CN201610379258 A CN 201610379258A CN 105887200 A CN105887200 A CN 105887200A
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crystal
laser
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张园园
王旭平
吕宪顺
刘冰
杨玉国
魏磊
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New Material Institute of Shandong Academy of Sciences
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    • 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
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
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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
    • H01S3/1601—Solid materials characterised by an active (lasing) ion
    • H01S3/1603—Solid materials characterised by an active (lasing) ion rare earth
    • H01S3/161—Solid materials characterised by an active (lasing) ion rare earth holmium

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Abstract

A kind of thulium holmium is co-doped with gallic acid strontium lanthanum laser crystal, manufacturing method and its application, the chemical formula of the crystal are as follows: Tm, Ho:SrLaGa3O7 belong to tetragonal crystal system, and space group is The crystal is with SrCO3, La2O3, Ga2O3, Tm2O3 and Ho2O3 is that raw material is grown according to czochralski method, the crystal is for being used as working-laser material in solid state laser, use laser diode or ti sapphire laser as pumping source, excitation generates that 2 mu m wavebands are continuous, tunable and ultrashort pulse laser output. To realize the transmitting of 2 mu m waveband lasers.

Description

A kind of thulium holmium is co-doped with gallic acid strontium lanthanum laser crystal, manufacture method and application thereof
Technical field
The present invention relates to ultrafast laser crystal Material Field, particularly relate to a kind of thulium holmium and be co-doped with gallic acid strontium lanthanum laser crystal, manufacture method and application thereof.
Background technology
2 μm laser cover human eye safe waveband; characteristics of atmospheric transmission is good; cover hydrone and the absorption band of CO2 molecule, in fields such as laser radar, therapeutic treatment, environmental conservation, Molecular Spectroscopy and for new middle-infrared band laser pumping source, all there is highly important using value.(pulsewidth is 10 to 2 mu m waveband ultrafast pulses-12-10-15S) there is the features such as extremely short persistent period, very high peak power, the widest spectrum, scientific research and social development are had important value and far reaching significance.
Summary of the invention
The present invention proposes a kind of thulium holmium and is co-doped with gallic acid strontium lanthanum laser crystal, it is achieved 2 mu m waveband lasers are launched.
To achieve these goals, the scheme that the present invention uses is:
A kind of thulium holmium is co-doped with gallic acid strontium lanthanum laser crystal, and the chemical formula of described crystal is: Tm, Ho:SrLaGa3O7, belonging to tetragonal crystal system, space group is。
Described Tm is Tm3+, described Tm3+Doping content 2～10at%；Described Ho is Ho3+, described Ho3+Doping content 0.4～1at%.
A kind of thulium holmium is co-doped with the preparation method of gallic acid strontium lanthanum laser crystal, it is characterized in that, including step:
1), SrCO is used3, La2O3, Ga2O3, Tm2O3And Ho2O3For raw material, according to reaction equation: 2SrCO3+(1-x-y)La2O3+3Ga2O3+xTm2O3+yHo2O3=2SrLa(1-x-y)TmxHoyGa3O7+2CO2Mol ratio in ↑ carries out proportioning, the most again by Ga2O3It is added according to the ratio of 1wt.%, and by all raw material mix homogeneously；Wherein 0.02≤x≤0.1,0.004≤y≤0.01；
2), the raw material after mix homogeneously is placed in platinum crucible, Isothermal sinter 10 hours at a temperature of 950 DEG C, then the raw mill of sintering, briquetting, then be placed in platinum crucible, sintering 10 hours in Muffle furnace, through solid state reaction kinetics Tm, Ho:SrLaGa3O7Crystalline polymorphic material；
3), polycrystal material be placed in Iridium Crucible, load single crystal pulling stove, pumping high vacuum, be filled with nitrogen protection atmosphere, Frequency Induction Heating, lower seed crystal carries out crystal growth；
4), it is cooled to room temperature after crystal growth, comes out of the stove；The crystal annealing come out of the stove is processed.
Described step 2) in Muffle furnace in the temperature of sintering be 1050 DEG C～1150 DEG C.
Described step 3) in environment of crystal growth be: growth temperature is 1600 DEG C, and crystal pull speed is 0.6-1 mm hr, and rotary speed is 15-20 rev/min.
Described step 4) in cooling rate of temperature fall be: 30 DEG C/h.
Described step 4) in annealing step be: the crystal come out of the stove is placed in electric furnace annealing, and annealing temperature is 950 DEG C～1050 DEG C, and annealing time is 8～10 hours.
A kind of right thulium holmium is co-doped with the application of gallic acid strontium lanthanum laser crystal, described crystal is used in solid state laser as working-laser material, use laser diode or ti sapphire laser as pumping source, excite generation 2 mu m wavebands continuous, tunable and the laser output of ultrashort pulse.The invention have the benefit that employing Tm3+And Ho3+Co-doped system, Tm3+Make sensitized ions, Ho3+For active ions, improve laser delivery efficiency, utilize locked mode element, it is achieved 2um mode-locked laser efficiently exports.
Accompanying drawing explanation
Figure 1Crystallogram is grown for embodiment 2.
Figure 2Continuously adjustable laser aid.
Figure 3 It is 2uM modulus-locking laser device.
Wherein, 1 laser diode, 2 collimating mirrors, 3 focus lamps, 4 input plane mirrors, 41 input plano-concave mirrors, 5 laser mediums, 6 birefringent filters, 7 plano-concave output coupling mirrors, 8 ti sapphire lasers, 9 plano-concaves high anti-focus lamp, 10 plano-concave high reflective mirrors, 11 locked mode elements, 12 output coupling mirrors.
Detailed description of the invention
In order to be better understood by technical scheme, below in conjunction withAccompanying drawingThe invention will be further described.
Trivalent rare earth ions Tm3+And Ho3+Stimulated radiation can launch the laser of 2 mu m wavebands: Tm laser instrument (3F4→3H6) near 1.9 μm, Ho laser instrument (5I7→5I8) near 2.1 μm, and both of which is quasi three level laser.Due to Ho3+Stimulated emission cross section big, fluorescence lifetime is long, therefore, mixes Ho3+Solid-state laser has unique advantage at 2um wave band of laser.But mix Ho at present3+Laser crystal does not also have suitable laser diode pumping source, usually uses Tm3+Ion laser resonance pumping realizes laser output.Tm3+The light of 800nm (AlGaAs) and 900nm (InGaAs) wave band there is is stronger absorption, improves semiconductor pumped absorption efficiency.Therefore, by Tm3+And Ho3+Directly co-doped is in a certain crystal substrate, Tm3+Make sensitized ions, Ho3+For active ions, make the transmission of the energy between particle and cross-relaxation complete at same its content, thus simplify laser structure, it is achieved high-efficiency operation, the purpose of raising laser delivery efficiency.2010, the reported first such as A.A.Lagatsky Tm, Ho codope NaY (WO4)2The laser output of crystal 191fs, the Output of laser mean power at 2060nm reaches 82Mw (Optics Latters, 35 (2010), 3027).The same year, in the YAG crystal of Tm, Ho codope, utilizing semiconductor quantum well to achieve the passive mode-locking output of 60ps, the average output power at 2.091um is 160mw, and repetition rate is 106.5MHz (Optics Express, 18 (2010), 6537).
The present invention uses czochralski method to carry out crystal growth, uses SrCO3, La2O3, Ga2O3, Tm2O3And Ho2O3For raw material, reactive chemistry formula is:
2SrCO3+(1-x-y)La2O3+3Ga2O3+xTm2O3+yHo2O3=2SrLa(1-x-y)TmxHoyGa3O7+2CO2↑
Embodiment 1:SrLa0.976Tm0.02Ho0.004Ga3O7The preparation (x=0.02, y=0.004) of crystal
Use SrCO3, La2O3, Ga2O3, Tm2O3And Ho2O3High pure raw material (purity is 99.999%), according to chemical equation:
SrCO3+0.488La2O3+1.5Ga2O3+0.01Tm2O3+0.002Ho2O3=SrLa0.976Tm0.02Ho0.004Ga3O7+CO2↑ stoichiometrically prepare growth Tm, Ho:SrLaGa3O7Raw material (the wherein Ga of crystal2O3Excess 1wt.%).1wt.% refers to one of percentage of each raw material gross mass.The raw material of preparation is placed in platinum crucible, sinters 10 hours, then the raw mill of sintering, briquetting, then be placed in platinum crucible at a temperature of 950 DEG C, and in Muffle furnace, 1050 DEG C sinter 10 hours, solid state reaction kinetics Tm, Ho:SrLaGa3O7Polycrystal material.Tm, Ho:SrLaGa3O7Polycrystal material is placed in Iridium Crucible, single crystal growing furnace evacuation, fills protection nitrogen.It is warming up to 1600 DEG C, after making material the most melt-blended, puts down the Tm in c direction, Ho:SrLaGa3O7Seed crystal, starts to grow crystal, and crystal pull rate is 1 mm hr, and rotary speed is 15 revs/min, obtains Tm, Ho:SrLaGa3O7Crystal, crystal perfection is without cracking.
Tm, Ho:SrLaGa growth3O7Crystal is placed in resistance furnace annealing, and annealing temperature is 950 DEG C, and annealing time is 8 hours, so can partly discharge the thermal stress produced in growth crystallization process.
Embodiment 2:SrLa0.955Tm0.04Ho0.005Ga3O7The preparation (x=0.04, y=0.005) of crystal
Use SrCO3, La2O3, Ga2O3, Tm2O3And Ho2O3High pure raw material (purity is 99.999%), according to chemical equation:
SrCO3+0.4775La2O3+1.5Ga2O3+0.02Tm2O3+0.0025Ho2O3=SrLa0.955Tm0.04Ho0.005Ga3O7+CO2↑
Stoichiometrically preparation growth Tm, Ho:SrLaGa3O7Raw material (the wherein Ga of crystal2O3Excess 1wt.%).The raw material of preparation is placed in platinum crucible, sinters 10 hours, then the raw mill of sintering, briquetting, then be placed in platinum crucible at a temperature of 950 DEG C, and in Muffle furnace, 1060 DEG C sinter 10 hours, solid state reaction kinetics Tm, Ho:SrLaGa3O7Polycrystal material.Tm, Ho:SrLaGa3O7Polycrystal material is placed in Iridium Crucible, single crystal growing furnace evacuation, fills protection nitrogen.It is warming up to 1600 DEG C, after making material the most melt-blended, puts down the Tm in c direction, Ho:SrLaGa3O7Seed crystal, starts to grow crystal, and crystal pull rate is 0.9 mm hr, and rotary speed is 15 revs/min, obtains Tm, Ho:SrLaGa3O7Crystal, crystal perfection is without cracking.
Tm, Ho:SrLaGa growth3O7Crystal is placed in resistance furnace annealing, and annealing temperature is 970 DEG C, and annealing time is 8 hours, so can partly discharge the thermal stress produced in growth crystallization process.
Embodiment 3:SrLa0.952Tm0.04Ho0.008Ga3O7The preparation (x=0.04, y=0.008) of crystal
Use SrCO3, La2O3, Ga2O3, Tm2O3And Ho2O3High pure raw material (purity is 99.999%), according to chemical equation:
SrCO3+0.476La2O3+1.5Ga2O3+0.02Tm2O3+0.004Ho2O3=SrLa0.952Tm0.04Ho0.008Ga3O7+CO2↑
Stoichiometrically preparation growth Tm, Ho:SrLaGa3O7Raw material (the wherein Ga of crystal2O3Excess 1wt.%).The raw material of preparation is placed in platinum crucible, sinters 10 hours, then the raw mill of sintering, briquetting, then be placed in platinum crucible at a temperature of 950 DEG C, and in Muffle furnace, 1100 DEG C sinter 10 hours, solid state reaction kinetics Tm, Ho:SrLaGa3O7Polycrystal material.Tm, Ho:SrLaGa3O7Polycrystal material is placed in Iridium Crucible, single crystal growing furnace evacuation, fills protection nitrogen.It is warming up to 1600 DEG C, after making material the most melt-blended, puts down the Tm in c direction, Ho:SrLaGa3O7Seed crystal, starts to grow crystal, and crystal pull rate is 0.8 mm hr, and rotary speed is 16 revs/min, obtains Tm, Ho:SrLaGa3O7Crystal, crystal perfection is without cracking.
Tm, Ho:SrLaGa growth3O7Crystal is placed in resistance furnace annealing, and annealing temperature is 970 DEG C, and annealing time is 8 hours, so can partly discharge the thermal stress produced in growth crystallization process.
Embodiment 4:SrLa0.932Tm0.06Ho0.008Ga3O7The preparation (x=0.06, y=0.008) of crystal
Use SrCO3, La2O3, Ga2O3, Tm2O3And Ho2O3High pure raw material (purity is 99.999%), according to chemical equation:
SrCO3+0.466La2O3+1.5Ga2O3+0.03Tm2O3+0.004Ho2O3=SrLa0.932Tm0.06Ho0.008Ga3O7+CO2↑
Stoichiometrically preparation growth Tm, Ho:SrLaGa3O7Raw material (the wherein Ga of crystal2O3Excess 1wt.%).The raw material of preparation is placed in platinum crucible, sinters 10 hours, then the raw mill of sintering, briquetting, then be placed in platinum crucible at a temperature of 950 DEG C, and in Muffle furnace, 1100 DEG C sinter 10 hours, solid state reaction kinetics Tm, Ho:SrLaGa3O7Polycrystal material.Tm, Ho:SrLaGa3O7Polycrystal material is placed in Iridium Crucible, single crystal growing furnace evacuation, fills protection nitrogen.It is warming up to 1600 DEG C, after making material the most melt-blended, puts down the Tm in c direction, Ho:SrLaGa3O7Seed crystal, starts to grow crystal, and crystal pull rate is 0.7 mm hr, and rotary speed is 16 revs/min, obtains Tm, Ho:SrLaGa3O7Crystal, crystal perfection is without cracking.
Tm, Ho:SrLaGa growth3O7Crystal is placed in resistance furnace annealing, and annealing temperature is 1000 DEG C, and annealing time is 9 hours, so can partly discharge the thermal stress produced in growth crystallization process.
Embodiment 5:SrLa0.912Tm0.08Ho0.008Ga3O7The preparation (x=0.08, y=0.008) of crystal
Use SrCO3, La2O3, Ga2O3, Tm2O3And Ho2O3High pure raw material (purity is 99.999%), according to chemical equation:
SrCO3+0.456La2O3+1.5Ga2O3+0.04Tm2O3+0.004Ho2O3=SrLa0.912Tm0.08Ho0.008Ga3O7+CO2↑
Stoichiometrically preparation growth Tm, Ho:SrLaGa3O7Raw material (the wherein Ga of crystal2O3Excess 1wt.%).The raw material of preparation is placed in platinum crucible, sinters 10 hours, then the raw mill of sintering, briquetting, then be placed in platinum crucible at a temperature of 950 DEG C, and in Muffle furnace, 1120 DEG C sinter 10 hours, solid state reaction kinetics Tm, Ho:SrLaGa3O7Polycrystal material.Tm, Ho:SrLaGa3O7Polycrystal material is placed in Iridium Crucible, single crystal growing furnace evacuation, fills protection nitrogen.It is warming up to 1600 DEG C, after making material the most melt-blended, puts down the Tm in c direction, Ho:SrLaGa3O7Seed crystal, starts to grow crystal, and crystal pull rate is 0.7 mm hr, and rotary speed is 18 revs/min, obtains Tm, Ho:SrLaGa3O7Crystal, crystal perfection is without cracking.
Tm, Ho:SrLaGa growth3O7Crystal is placed in resistance furnace annealing, and annealing temperature is 1000 DEG C, and annealing time is 9 hours, so can partly discharge the thermal stress produced in growth crystallization process.
Embodiment 6:SrLa0.94Tm0.05Ho0.01Ga3O7The preparation (x=0.05, y=0.01) of crystal
Use SrCO3, La2O3, Ga2O3, Tm2O3And Ho2O3High pure raw material (purity is 99.999%), according to chemical equation:
SrCO3+0.47La2O3+1.5Ga2O3+0.025Tm2O3+0.005Ho2O3=SrLa0.94Tm0.05Ho0.01Ga3O7+CO2↑
Stoichiometrically preparation growth Tm, Ho:SrLaGa3O7Raw material (the wherein Ga of crystal2O3Excess 1wt.%).The raw material of preparation is placed in platinum crucible, sinters 10 hours, then the raw mill of sintering, briquetting, then be placed in platinum crucible at a temperature of 950 DEG C, and in Muffle furnace, 1120 DEG C sinter 10 hours, solid state reaction kinetics Tm, Ho:SrLaGa3O7Polycrystal material.Tm, Ho:SrLaGa3O7Polycrystal material is placed in Iridium Crucible, single crystal growing furnace evacuation, fills protection nitrogen.It is warming up to 1600 DEG C, after making material the most melt-blended, puts down the Tm in c direction, Ho:SrLaGa3O7Seed crystal, starts to grow crystal, and crystal pull rate is 0.6 mm hr, and rotary speed is 18 revs/min, obtains Tm, Ho:SrLaGa3O7Crystal, crystal perfection is without cracking.
Tm, Ho:SrLaGa growth3O7Crystal is placed in resistance furnace annealing, and annealing temperature is 1050 DEG C, and annealing time is 10 hours, so can partly discharge the thermal stress produced in growth crystallization process.
Embodiment 7:SrLa0.89Tm0.1Ho0.01Ga3O7The preparation (x=0.1, y=0.01) of crystal
Use SrCO3, La2O3, Ga2O3, Tm2O3And Ho2O3High pure raw material (purity is 99.999%), according to chemical equation:
SrCO3+0.445La2O3+1.5Ga2O3+0.05Tm2O3+0.005Ho2O3=SrLa0.89Tm0.1Ho0.01Ga3O7+CO2↑
Stoichiometrically preparation growth Tm, Ho:SrLaGa3O7Raw material (the wherein Ga of crystal2O3Excess 1wt.%).The raw material of preparation is placed in platinum crucible, sinters 10 hours, then the raw mill of sintering, briquetting, then be placed in platinum crucible at a temperature of 950 DEG C, and in Muffle furnace, 1150 DEG C sinter 10 hours, solid state reaction kinetics Tm, Ho:SrLaGa3O7Polycrystal material.Tm, Ho:SrLaGa3O7Polycrystal material is placed in Iridium Crucible, single crystal growing furnace evacuation, fills protection nitrogen.It is warming up to 1600 DEG C, after making material the most melt-blended, puts down the Tm in c direction, Ho:SrLaGa3O7Seed crystal, starts to grow crystal, and crystal pull rate is 0.6 mm hr, and rotary speed is 20 revs/min, obtains Tm, Ho:SrLaGa3O7Crystal, crystal perfection is without cracking.
Tm, Ho:SrLaGa growth3O7Crystal is placed in resistance furnace annealing, and annealing temperature is 1050 DEG C, and annealing time is 10 hours, so can partly discharge the thermal stress produced in growth crystallization process.
In embodiment 1-7, the crystal of generationSuch as figure 1Shown in, the chemical formula of described crystal is: Tm, Ho:SrLaGa3O7, described crystal belongs to tetragonal crystal system, and space group is.Described Tm is Tm3+, described Tm3+Doping content 2～10at%；Described Ho is Ho3+, described Ho3+Doping content 0.4～1at%.It is 1% that 1at% refers to mole doping content.
In embodiment 1-7, the crystal generated first being down to room temperature and makes annealing treatment, the speed of cooling is 30 DEG C/h.
Embodiment 8:2um continuously adjustable laser exports
By Tm, Ho:SrLaGa obtained in embodiment 1-73O7Crystal, pressesAccompanying drawing 2Shown in be placed on the position of 5, laser beam incides Tm, Ho:SrLaGa through focusing system3O7In laser diode, obtain the output of 2um continuously adjustable laser.
Figure 2For continuously adjustable laser output device, including laser diode 1, collimating mirror 2, focus lamp 3, input plane mirror 4, laser medium 5, birefringent filter 6, plano-concave output coupling mirror 7.
Pumping source is laser diode, and resonator cavity input mirror one end plating pumping wavelength anti-reflection film, other end plating pumping wavelength is anti-reflection and the deielectric-coating of gain wavelength height reflection.Laser medium plating pumping wavelength and the anti-reflection deielectric-coating of gain wavelength, improve output performance of laser.The deielectric-coating of output coupling mirror plating 2um fractional transmission, transmitance is 1.5%, 3% and 5%.
Embodiment 9:2um ultra-short pulse laser exports
By Tm, Ho:SrLaGa obtained in embodiment 1-73O7Crystal, pressesAccompanying drawing 3Shown in be placed on the position of 5, obtain 2um mode-locked laser output.
Figure 3For ultra-short pulse laser output device, including: ti sapphire laser 8, focus lamp 3, input plano-concave mirror 41, laser medium 5, the high anti-focus lamp 9 of plano-concave, plano-concave high reflective mirror 10, locked mode element 11 and output coupling mirror 12.
Pumping source is ti sapphire laser, and peak power output is more than 3 watts.Input plano-concave mirror one end plating pumping wavelength anti-reflection film, other end plating pumping wavelength is anti-reflection and the deielectric-coating of gain wavelength height reflection.Plano-concave high reflective mirror and the deielectric-coating of plano-concave high anti-focus lamp plating gain wavelength height reflection, the deielectric-coating of output coupling mirror plating gain wavelength fractional transmission, transmitance is 1.5%, 3% and 5%.For improving output performance of laser, laser medium is put by Brewster angle.
SrLaGa3O7Crystal has melilite structure, dopant ion Tm3+And Ho3+Replace La3+Ion, forms activation centers different in many structures, causes spectrum to include the inhomogeneous broadening of absorption spectrum and emission spectrum, and stimulated emission cross section is reduced in host crystal.Wide absorption spectrum, substantially increases the utilization rate of excitation energy；And the wide spectral line of emission produces locked mode (especially femtosecond pulse) laser and is dreamed of.The gallic acid strontium lanthanum crystallophy excellent performance of thulium holmium codope, is a kind of preferably 2um ultrafast laser crystal, for Tm, Ho:SrLaGa3O7Crystal yet there are no report.
Combine although above-mentionedAccompanying drawingThe detailed description of the invention of the present invention is described; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme, those skilled in the art need not to pay various amendments or deformation that creative work can make still within protection scope of the present invention.

Claims (8)

1. thulium holmium is co-doped with a gallic acid strontium lanthanum laser crystal, it is characterized in that, the change of described crystal Formula is: Tm, Ho:SrLaGa3O7, belonging to tetragonal crystal system, space group is
2. a kind of thulium holmium as claimed in claim 1 is co-doped with gallic acid strontium lanthanum laser crystal, and it is special Levying and be, described Tm is Tm3+, described Tm3+Doping content 2～10at%；Described Ho is Ho3+, described Ho3+Doping content 0.4～1at%.
3. the thulium holmium described in claim 1-2 is co-doped with the preparation of gallic acid strontium lanthanum laser crystal Method, is characterized in that, described crystal uses Czochralski grown, including step:
1), SrCO is used3, La2O3, Ga2O3, Tm2O3And Ho2O3For raw material, according to reaction equation: 2SrCO3+(1-x-y)La2O3+3Ga2O3+xTm2O3+yHo2O3=2SrLa(1-x-y)TmxHoyGa3O7+2CO2↑ In mol ratio carry out proportioning, the most again by Ga2O3It is added according to 1wt% ratio, and will All raw material mix homogeneously；Wherein 0.02≤x≤0.1,0.004≤y≤0.01；
2), the raw material after mix homogeneously is placed in platinum crucible, at a temperature of 950 DEG C Isothermal sinter 10 hours, then the raw mill of sintering, briquetting, then is placed into platinum earthenware In crucible, sintering 10 hours in Muffle furnace, through solid state reaction kinetics Tm, Ho:SrLaGa3O7 Crystalline polymorphic material；
3), polycrystal material be placed in Iridium Crucible, load single crystal pulling stove, pumping high vacuum, be filled with Nitrogen protection atmosphere, Frequency Induction Heating, lower seed crystal carries out crystal growth；
4), it is cooled to room temperature after crystal growth, comes out of the stove；The crystal annealing come out of the stove is processed.
A kind of thulium holmium the most as claimed in claim 3 is co-doped with the preparation of gallic acid strontium lanthanum laser crystal Method, is characterized in that, described step 2) in Muffle furnace in the temperature of sintering be 1050 DEG C～ 1150℃。
A kind of thulium holmium the most as claimed in claim 3 is co-doped with the preparation of gallic acid strontium lanthanum laser crystal Method, is characterized in that, described step 3) in environment of crystal growth be: growth temperature is 1600 DEG C, crystal pull speed is 0.6-1 mm hr, and rotary speed is 15-20 rev/min.
6. a kind of thulium holmium as described in claim 3 or 4 is co-doped with gallic acid strontium lanthanum laser crystal Preparation method, is characterized in that, described step 4) in cooling rate of temperature fall be: 30 DEG C/little Time.
7. a kind of thulium holmium as described in claim 3 or 4 is co-doped with gallic acid strontium lanthanum laser crystal Preparation method, is characterized in that, described step 4) in annealing step be: the crystalline substance come out of the stove Body is placed in electric furnace annealing, and annealing temperature is 950 DEG C～1050 DEG C, and annealing time is 8～10 Hour.
8. the thulium holmium described in claim 1-2 is co-doped with an application for gallic acid strontium lanthanum laser crystal, It is characterized in that, described crystal as working-laser material, uses laser in solid state laser Diode or ti sapphire laser, as pumping source, excite generation 2 mu m wavebands continuous, adjustable Humorous and ultrashort pulse laser exports.
CN201610379258.6A 2016-05-31 2016-05-31 Thulium-holmium-codoped strontium lanthanum gallate laser crystal, preparation method and application of crystal Pending CN105887200A (en)

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