CN1292105C - Sodium and ytterbium doped calcium fluoride laser crystal and growth method thereof - Google Patents

Sodium and ytterbium doped calcium fluoride laser crystal and growth method thereof Download PDF

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CN1292105C
CN1292105C CN 200410089020 CN200410089020A CN1292105C CN 1292105 C CN1292105 C CN 1292105C CN 200410089020 CN200410089020 CN 200410089020 CN 200410089020 A CN200410089020 A CN 200410089020A CN 1292105 C CN1292105 C CN 1292105C
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crystal
caf
calcium fluoride
atmosphere
crucible
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CN1635192A (en
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徐军
苏良碧
李红军
董永军
赵广军
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Shanghai Institute of Optics and Fine Mechanics of CAS
Shanghai Micro Electronics Equipment Co Ltd
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Abstract

The present invention relates to a laser crystal codoped by sodium and yttrium calcium fluoride and a growing method thereof, wherein the crystal has the molar ratio formula of the raw material satisfies that CaF2: YbF3: NaF: PbF2 = 1: (0.005 to 0.2): (0.0005 to 0.2): (0 to 0.01). A Yb and Na: CaF2 single crystal is grown by adopting a melting method, all raw materials are weighed according to the proportion of a selected formula, and are pressed into blocks after being thoroughly and uniformly mixed; the blocks are loaded in a crucible, and are grown by adopting the melting method. The crystal grown by adopting the present invention simultaneously introduces Yb<3+> and Na<+>, when Ca<2+> is replaced by Na<+> and Yb<3+>, the complementation of electric charge is formed so as to reach the charge balance of a system; simultaneously, the present invention has the action of preventing the structure of a Yb<3+> group cluster and the formation of Yb<2+>, and greatly improves the luminous intensity and the fluorescence lifetime of the system.

Description

Mix sodium and ytterbium calcium fluoride laser crystal and growth method thereof altogether
Technical field
The present invention relates to CaF 2Crystal, particularly a kind of Yb 3+And Na +The CaF that mixes altogether 2Laser crystals and growth method thereof, this Yb, Na:CaF 2The luminous efficiency of single crystal and fluorescence lifetime are higher than widely singly mixes Yb 3+: CaF 2Crystal.This crystal can be used as the working-laser material of high-level efficiency, high energy storage.
Background technology
Because the high luminescent properties of InGaAs laser diode (LD) in 0.9～1.1 micron wave length scope, people are to Yb 3+Adulterated material is as the research interest sustainable growth of high-level efficiency and high-power laser system.Yb 3+Ion makes it have unusual quantum defective (＜10%) in simple two level structures near infrared spectrum zone, thereby reduces the thermal load in the laser operation, avoids changing and adverse effect such as excited state absorption.Relevant research work mainly concentrates on Yb in the past 3+Adulterated oxide compound laser host, for example Yb 3Al 5O 12(YAG), Ca 5(PO 4) 3F (FAP), Y 2SiO 5(YSO) etc., referring to Opt.Lett.1991,16:1089; IEEE J.Quantum Electron.1994,30:170; Optical Mater.2002,19:81.Compare with oxide compound, fluorochemical has following superior character: the transmittance from the vacuum ultraviolet (VUV) to the infrared wavelength range is very high, low specific refractory power can limit the non-linear effect under the high intensity laser beam pumping effect, and low phonon energy reduces the non-radiative relaxation between the adjacent energy level.
In the various fluorochemicals, CaF 2Has lower phonon energy (328cm -1), high thermal conductivity (10Wm -1K -1), and be easy to grow into large size single crystal.Recently, Yb:CaF 2The crystalline laser activity has been subjected to people's attention, referring to Appl.Phys.B 2004,78:681; Opt.Lett.2004,29:1879 has obtained the LD pumping laser output of high power tunable, and wavelength tuning range is 1018～1072nm.The adulterated CaF of trivalent rare earth ions 2Crystalline case structure and spectrum property are furtherd investigate, and the multiple charge compensation mode that charge differences causes produces complicated multiple symmetry centre, cause this system have can with glassy phase wide absorption and emmission spectrum relatively.These characteristics are tunable for producing, the laser output of short pulse is favourable, but also must reduces laser output power.And trivalent rare earth ions is at CaF 2Be very easy to form the cluster structure in the lattice.For example, doping content is the Er:CaF of 0.05at% 2Just can observe Er in the crystal 3+The existence of ion pair, referring to J.Chem.Phys.1976,65:510.Such cluster structure is a class fluorescent quenching center.Especially, for the Yb ion, its outer electronic structure tends to be full of the 4f shell, forms stable 4f 14(Yb 2+) structure.Particularly enter CaF 2Replace Ca in the lattice 2+, easier form with divalence exists, thereby reduces active ions Yb 3+Effective concentration.
In sum, the Yb:CaF of LD pumping 2Crystal has obtained interesting laser activity at present, if can avoid Yb 3+Cluster structure and Yb 2+Formation, will improve the laser activity of this material significantly.
Summary of the invention
Main purpose of the present invention provides a kind of sodium and ytterbium calcium fluoride laser crystal and growth method thereof of mixing altogether, to improve Yb 3+: CaF 2The crystalline luminous efficiency.
Gordian technique of the present invention is at CaF 2Introduce Yb in the matrix simultaneously 3+And Na +, Na +And Yb 3+Replacing Ca 2+The time form the electric charge complementation to reach the charge balance of system, play simultaneously and stop Yb 3+Cluster structure and Yb 2+The effect that forms, thus the luminous intensity and the fluorescence lifetime of this system improved widely.
Specific embodiment of the present invention is as follows:
A kind of sodium and ytterbium calcium fluoride laser crystal and growth method thereof of mixing altogether is characterized in:
＜1〉composition of raw materials:
Initial feed adopts YbF 3, NaF, CaF 2And PbF 2, first three is planted raw material and equals x: y in molar ratio: 1 prepares burden, and wherein x equals 0.005～0.2, and y equals 0.0005～0.2, PbF 2Add-on be 0～0.01mol, preferable range is 0.002～0.004mol.
＜2〉adopt melt method for growing Yb, Na:CaF 2Single crystal
By above-mentioned＜1〉in formula rate take by weighing all raw materials, thorough mixing is the back briquetting evenly, in the crucible of packing into then, adopts the above-mentioned single crystal of melt method for growing.
For crystal pulling method, crucible material is an iridium, and it is the CaF of [111] that seed crystal adopts through X-ray diffractometer accurate pointing normal line of butt end direction 2Single crystal rod, crystal growth is at high-purity Ar atmosphere or fluorine-containing atmosphere (CF 4Or HF) carries out in.
For falling crucible method or temperature gradient method, crucible material adopts high purity graphite, and crucible bottom can not put seed crystal, or puts into the CaF described in the above-mentioned crystal pulling method 2Single crystal rod, crystal growth is at high-purity Ar atmosphere or fluorine-containing atmosphere (CF 4Or HF) carries out in.
The present invention is Yb 3+And Na +The CaF that mixes altogether 2Laser crystals, this crystalloid have high luminous efficiency and long fluorescence lifetime, can be used for developing LD pumping all-solid-state laser efficiently.
Description of drawings
Figure 1 shows that the Yb that records under the same terms, Na:CaF 2And Yb:CaF 2The contrast of crystal emmission spectrum.
Among the figure: curve a represents singly to mix Yb (2.0at%): CaF 2Crystal;
Curve b represents Yb (2at%), Na (3at%): CaF 2Crystal;
Curve c represents Yb (2at%), Na (20at%): CaF 2Crystal.
Figure 2 shows that the Yb that records under the same terms, Na:CaF 2And Yb:CaF 2Crystal excites 1030nm fluorescence intensity extinction curve in time down at LD940nm.
Among the figure: curve a represents singly to mix Yb (2.0at%): CaF 2Crystal;
Curve b represents Yb (2at%), Na (3at%): CaF 2Crystal;
Curve c represents Yb (2at%), Na (20at%): CaF 2Crystal.
Embodiment
Specific embodiment of the present invention is as follows:
＜1〉composition of raw materials
Initial feed adopts YbF 3, NaF, CaF 2And PbF 2, first three is planted raw material and equals x: y in molar ratio: 1 prepares burden, and wherein x equals 0.005～0.2, and y equals 0.0005～0.2, PbF 2Add-on be 0～0.01mol, preferable range is 0.002～0.004mol.
＜2〉adopt melt method for growing Yb, Na:CaF 2Single crystal
By above-mentioned＜1〉in formula rate take by weighing all raw materials, thorough mixing is the back briquetting evenly, in the crucible of packing into then, adopts the above-mentioned single crystal of melt method for growing.
For crystal pulling method, crucible material is an iridium, and it is the CaF of [111] that seed crystal adopts through X-ray diffractometer accurate pointing normal line of butt end direction 2Single crystal rod, crystal growth is at high-purity Ar atmosphere or fluorine-containing atmosphere (CF 4Or HF) carries out in.
For falling crucible method or temperature gradient method, crucible material adopts high purity graphite, and crucible bottom can not put seed crystal, or puts into the CaF described in the above-mentioned crystal pulling method 2Single crystal rod, crystal growth is at high-purity Ar atmosphere or fluorine-containing atmosphere (CF 4Or HF) carries out in.
Embodiment 1: Czochralski grown [Yb (0.5at%), Na (2.5at%): CaF 2] crystal
Press YbF 3, NaF, CaF 2Mol ratio be to take by weighing raw material at 0.005: 0.025: 1, add the PbF that molar content equals 0.01mol then 2As Oxygen Scavenger, mix back briquetting on hydropress, be put in the iridium crucible, adopt Czochralski grown crystal, it is the CaF of [111] that seed crystal adopts through X-ray diffractometer accurate pointing normal line of butt end direction 2Single crystal rod, crystal growth is carried out in high-purity Ar atmosphere.
Embodiment 2: warm terraced method growth [Yb (2at%), Na (3at%): CaF 2] crystal
Press YbF 3, NaF, CaF 2Mol ratio be to prepare burden at 0.02: 0.03: 1, mix back briquetting on hydropress, be put in the plumbago crucible, crucible bottom does not have seed crystal.Adopt temperature gradient method, growing crystal in high-purity Ar atmosphere.The crystal-cut of being grown is in blocks, on the Triax550 fluorescence spectrophotometer, test curve b among room temperature emmission spectrum such as Fig. 1 behind the optical polish, it is the InGaAs laser diode of 940nm that pumping source adopts wavelength.Its fluorescence intensity is with respect to Yb (2at%): CaF 2(curve a) improves several times to crystal among Fig. 1.Adopt Tektronix TDS3052 digital oscilloscope record 1030nm fluorescence intensity extinction curve in time, obtain fluorescence lifetime numerical value by single order exponential attenuation equation model experimental data.Curve a among Fig. 2 is respectively the Yb (2at%) that records under the same terms, Na (3at%): CaF shown in the b 2And Yb (2at%): CaF 2Crystal excites 1030nm fluorescence intensity extinction curve in time down at LD940nm, simulates fluorescence lifetime and equals 0.74ms and 1.94ms respectively.
Embodiment 3: warm terraced method growth [Yb (2at%), Na (20at%): CaF 2] crystal
Press YbF 3, NaF, CaF 2Mol ratio be to take by weighing raw material at 0.02: 0.2: 1, add the PbF that molar content is 0.7at% then 2As Oxygen Scavenger.Raw material mixes back briquetting on hydropress, is put in the plumbago crucible, and crucible bottom is placed with through the CaF of X-ray diffractometer accurate pointing normal line of butt end direction for [111] 2Single crystal rod is as seed crystal.The plumbago crucible that installs raw material is put into temperature gradient furnace, growing crystal in high-purity Ar atmosphere.The crystal-cut of being grown is in blocks, on the Triax550 fluorescence spectrophotometer, test curve c among room temperature emmission spectrum such as Fig. 1 behind the optical polish, it is the InGaAs laser diode of 940nm that pumping source adopts wavelength.Its fluorescence intensity is with respect to Yb (2at%), Na (3at%): CaF 2Crystal (curve b among Fig. 1) further improves.Adopt TektronixTDS3052 digital oscilloscope record 1030nm fluorescence intensity extinction curve in time, obtain fluorescence lifetime numerical value by single order exponential attenuation equation model experimental data.Curve c is depicted as this crystal and excites 1030nm fluorescence intensity extinction curve in time down at LD940nm among Fig. 2, simulates fluorescence lifetime and equals 7.20ms respectively.
Embodiment 4: Bridgman-Stockbarge method for growing [Yb (5at%), Na (10at%): CaF 2] crystal
Press YbF 3, NaF, CaF 2Mol ratio be to take by weighing raw material at 0.05: 0.1: 1, add the PbF that molar content equals 0.3at% then 2As Oxygen Scavenger.Raw material mixes back briquetting on hydropress, is put in the plumbago crucible, and crucible bottom is placed with through the CaF of X-ray diffractometer accurate pointing normal line of butt end direction for [111] 2Single crystal rod is as seed crystal.The plumbago crucible that installs raw material is put into crucible decline stove, growing crystal in high-purity Ar atmosphere.
Embodiment 5: Czochralski grown [Yb (10at%), Na (15at%): CaF 2] crystal
Press YbF 3, NaF, CaF 2Mol ratio be to take by weighing raw material at 0.1: 0.15: 1, add the PbF that molar content is 0.6at% then 2As Oxygen Scavenger.Raw material mixes back briquetting on hydropress, is put in the iridium crucible, adopts Czochralski grown crystal, and it is the CaF of [111] that seed crystal adopts through X-ray diffractometer accurate pointing normal line of butt end direction 2Single crystal rod, crystal growth is carried out in high-purity Ar atmosphere.
Embodiment 6: Bridgman-Stockbarge method for growing [Yb (20at%), Na (2at%): CaF 2] crystal
Press YbF 3, NaF, CaF 2Mol ratio be to take by weighing raw material at 0.2: 0.02: 1, mix back briquetting on hydropress, be put in the plumbago crucible, crucible bottom is placed with through the CaF of X-ray diffractometer accurate pointing normal line of butt end direction for [111] 2Single crystal rod is as seed crystal.The plumbago crucible that installs raw material is put into crucible decline stove, growing crystal in high-purity Ar atmosphere.
The test of emmission spectrum
With above-mentioned＜2〉growth Yb, Na:CaF 2The single crystal dicing is tested the room temperature emmission spectrum on the Triax550 fluorescence spectrophotometer behind the optical polish, it is the InGaAs laser diode of 940nm that pumping source adopts wavelength.Figure 1 shows that the Yb that records under the same terms, Na:CaF 2And Yb:CaF 2The contrast of crystal emmission spectrum.Curve a represents singly to mix Yb (2.0at%): CaF among the figure 2Crystal; Curve b represents Yb (2at%), Na (3at%): CaF 2Crystal; Curve c represents Yb (2at%), Na (20at%): CaF 2Crystal.As seen from the figure, with Na +The increase of mixed ratio, Yb:CaF 2The crystalline luminous intensity has improved significantly.
The test of fluorescence lifetime
Adopt Tektronix TDS3052 digital oscilloscope record 1030nm fluorescence intensity extinction curve in time, obtain fluorescence lifetime numerical value by single order exponential attenuation equation model experimental data.Figure 2 shows that the Yb that records under the same terms, Na:CaF 2And Yb:CaF 2Crystal excites 1030nm fluorescence intensity extinction curve in time down at LD940nm.Curve a represents singly to mix Yb (2.0at%): CaF among the figure 2Crystal; Curve b represents Yb (2at%), Na (3at%): CaF 2Crystal; Curve c represents Yb (2at%), Na (20at%): CaF 2Crystal.Single order exponential attenuation equation model goes out three kinds of crystalline fluorescence lifetimes and is respectively 0.74ms, 1.94ms and 7.20ms.This shows, with Na +The increase of mixed ratio, Yb:CaF 2Crystalline fluorescence lifetime increases significantly.

Claims (7)

1, a kind of sodium and ytterbium calcium fluoride laser crystal mixed altogether is characterized in that this crystalline composition of raw materials is as follows:
Form mol
CaF 2 1
YbF 3 0.005～0.2
NaF 0.0005～0.2
PbF 2 0～0.01。
2, sodium and the ytterbium calcium fluoride laser crystal mixed altogether according to claim 1 is characterized in that described PbF 2The scope of add-on be 0.002～0.004mol.
3, the described growth method of mixing sodium and ytterbium calcium fluoride laser crystal altogether of claim 1 is characterized in that adopting melt method for growing Yb, Na:CaF 2Single crystal is by selected each raw material YbF 3, CaF 2, and PbF 2Ratio after, take by weighing all raw materials in proportion, thorough mixing is the back briquetting evenly, in the crucible of packing into then, adopts the above-mentioned single crystal of melt method for growing.
4, growth method of mixing sodium and ytterbium calcium fluoride laser crystal altogether according to claim 3, when it is characterized in that adopting Czochralski grown crystal, crucible material is an iridium, it is the CaF of [111] that seed crystal adopts through X-ray diffractometer accurate pointing normal line of butt end direction 2Single crystal rod, crystal growth is carried out in high-purity Ar atmosphere or fluorine-containing atmosphere.
5, growth method of mixing sodium and ytterbium calcium fluoride laser crystal altogether according to claim 4 is characterized in that described fluorine gas atmosphere is CF 4Or the atmosphere of HF.
6, growth method of mixing sodium and ytterbium calcium fluoride laser crystal altogether according to claim 3, it is characterized in that adopting falling crucible method or temperature gradient method, crucible material adopts high purity graphite, crucible bottom can not put seed crystal, or employing is the CaF of [111] through X-ray diffractometer accurate pointing normal line of butt end direction 2Single crystal rod, crystal growth is carried out in high-purity Ar atmosphere or fluorine-containing atmosphere.
7, growth method of mixing sodium and ytterbium calcium fluoride laser crystal altogether according to claim 6 is characterized in that described fluorine gas atmosphere is CF 4Or the atmosphere of HF.
CN 200410089020 2004-12-02 2004-12-02 Sodium and ytterbium doped calcium fluoride laser crystal and growth method thereof Expired - Fee Related CN1292105C (en)

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CN111621849A (en) * 2020-05-25 2020-09-04 北京雷生强式科技有限责任公司 Magneto-optical crystal, magneto-optical device and preparation method
US20210408756A1 (en) * 2018-10-31 2021-12-30 Commissariat A L'energie Atomique Et Aux Energies Alternatives Laser crystal with at least two co-dopants

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CN101864596A (en) * 2010-07-02 2010-10-20 中国科学院上海光学精密机械研究所 Yb, Gd co-doped barium fluoride crystal and preparation method thereof
CN102534776A (en) * 2012-03-30 2012-07-04 中国科学院上海硅酸盐研究所 Neodymium ion doped fluoride laser crystal
CN103643301A (en) * 2013-12-20 2014-03-19 中国科学院上海硅酸盐研究所 Method for annealing large-size calcium fluoride crystal

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210408756A1 (en) * 2018-10-31 2021-12-30 Commissariat A L'energie Atomique Et Aux Energies Alternatives Laser crystal with at least two co-dopants
CN111621849A (en) * 2020-05-25 2020-09-04 北京雷生强式科技有限责任公司 Magneto-optical crystal, magneto-optical device and preparation method

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