CN101092745A - Laser crystal ErBa3B9O18 of borate, preparation method, and usage - Google Patents

Laser crystal ErBa3B9O18 of borate, preparation method, and usage Download PDF

Info

Publication number
CN101092745A
CN101092745A CN 200710098764 CN200710098764A CN101092745A CN 101092745 A CN101092745 A CN 101092745A CN 200710098764 CN200710098764 CN 200710098764 CN 200710098764 A CN200710098764 A CN 200710098764A CN 101092745 A CN101092745 A CN 101092745A
Authority
CN
China
Prior art keywords
erba
melt
laser
crystal
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN 200710098764
Other languages
Chinese (zh)
Inventor
陈小龙
何明
王皖燕
许燕萍
刘军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Physics of CAS
Original Assignee
Institute of Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Physics of CAS filed Critical Institute of Physics of CAS
Priority to CN 200710098764 priority Critical patent/CN101092745A/en
Publication of CN101092745A publication Critical patent/CN101092745A/en
Pending legal-status Critical Current

Links

Images

Landscapes

  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

This invention relates to borate laser crystal ErBa3B9O18, its preparation method and application in solid-state laser. The ErBa3B9O18 laser crystal is hexagonal system, and has a space group of P63/m. The unit cell parameters of the ErBa3B9O18 laser crystal are: a = b = 7.17-7.19 Aring and c = 16.98-17.00 Aring. The ErBa3B9O18 laser crystal has high doping concentration of activation ions, and high luminescence efficiency, and does not have sudden extinguish of luminescence concentration. The ErBa3B9O18 laser crystal has Er3+ as the luminescence center, and has such advantages as easy cutting, grinding, polishing and storage, no dissolution in water, no deliquescence, and high stability in air. The slice laser manufactured from the ErBa3B9O18 laser crystal has such advantages as low thickness, high power, small size and high compactness.

Description

A kind of borate laser crystal ErBa 3B 9O 18And its production and use
Technical field
The present invention relates to the laser crystals field, especially relate to a kind of borate laser crystal, its growth method and purposes that can be applicable to solid statelaser.
Background technology
Utilize the solid statelaser of laser diode pumped, particularly high-average power laser, have the efficient height, the life-span is long, compact construction, and advantage such as reliable and stable demonstrates more and more great application prospect in fields such as industry, scientific research and military affairs.With Er 3+Ion be the laser apparatus of operation material at optical communication, medical treatment, there is important use in fields such as range finding.The appearance of the laser apparatus of thin-disc laser medium is intended to solve many problems that the high average power solid laser device exists.For thin-sheet laser,,, just can improve heat deposition widely as long as reasonably design coupled system, laser medium configuration and effective coupled modes when pumping area size during much larger than sheet thickness.Thin-sheet laser adopts the end pumping structure, and pump light is intimate coaxial with resonator cavity, can improve assimilated efficiency greatly.Simultaneously, the laser medium configuration adopts thin slice, and the pumping area size is much larger than sheet thickness, and so just can make pumping light is that nearly flat-top distributes, hot-fluid just can be thought to distribute along the one dimension of sheet thickness direction, and radially temperature distribution is uniform in pumping area.Therefore, thin-sheet laser greatly reduces the thermal lensing effect and the thermic stress birefringence of medium, can calibrate and be amplified to very high mean power.At present, many working-laser materials, for example Nd:YVO 4, Er-Yb: glass, Yb:YAG etc. all are applied to the research of thin-sheet laser.Studies show that the thickness that reduces laser crystals helps promoting miniaturization of devices on the one hand, improves compact degree; On the other hand, can save crystalline material and help the heat radiation.And want to reduce further the thickness of thin-disc laser medium, and will guarantee higher power and efficient, must improve the concentration of the active ions in the laser medium for this reason.Therefore, it is imperative that exploration can be carried out the solid laser material of high-concentration dopant.Inst. of Physics, CAS's crystal growth group has been reported the borate compound of the powder phase of a series of isomorphisms in 2 004 years, consult document: Li, X.Z.; Wang, C.; Chen, X.L.; Li, H.; Jia, L.S.; Wu, L.; Du Y.X.; Xu, Y.P.Inorg.Chem.2004,43,8555.We are ErBa in a series of to this 3B 9O 18Compound has carried out crystal growth and luminosity research, finds that it is a kind of laser crystals that application prospect is arranged.
Summary of the invention
One of purpose of the present invention provides a kind of ErBa 3B 9O 18Laser crystals, the activated ion concentration in this crystal can be very big, so this crystal is suitable as the operation material of solid statelaser, particularly thin-sheet laser.
Another object of the present invention provides a kind of ErBa 3B 9O 18The preparation method of laser crystals.
To achieve these goals, the present invention has adopted following technical scheme:
The invention provides a kind of ErBa 3B 9O 18Laser crystals, it is a hexagonal system, spacer is P6 3/ m, unit cell parameters is a=b=7.17～7.19 ; C=16.98～17.00 .
ErBa provided by the invention 3B 9O 18Laser crystals is easy to processing, water insoluble and deliquescence not.
Wherein, preferred ErBa 3B 9O 18Laser crystals is a monocrystalline, and its size is not less than 1 * 1 * 0.5mm 3, preferred 3 * 3 * 1～15 * 12 * 4mm 3
The invention provides a kind of ErBa 3B 9O 18The preparation method of laser crystals, this method adopt melting method to carry out ErBa 3B 9O 18The growth of laser crystals.This melting method comprises the melt growth method that crystal pulling method, slow cooling method, warm terraced method etc. are conventional.
ErBa of the present invention 3B 9O 18The preferred crystal pulling method (Czochralski method) that adopts of one of melting method of laser crystals.Wherein, Czochralski grown ErBa 3B 9O 18Laser crystals specifically may further comprise the steps:
1) with solid state reaction synthetic ErBa 3B 9O 18Powder melts in crucible, and temperature of fusion is 1037 ℃-1042 ℃, and melt is heated up above about temperature of fusion 30-50 ℃;
2) seed crystal can obtain by utilizing platinum wire contact melt and slowly lowering the temperature;
3) following seed crystal makes seed crystal 0.5-2.0cm place preheating 10-30 minute above melt, makes seed crystal contact melt then;
4) carry out isodiametric growth then, wherein pulling rate is 0.02-1.0mm/h, and rotating speed is 10-50rpm;
5) growth is slowly cooled off after reaching desired size, obtains ErBa 3B 9O 18Laser crystals.
Another ErBa of the present invention 3B 9O 18The melting method of laser crystals is to adopt the slow cooling method, and it specifically may further comprise the steps:
1) with solid state reaction synthetic ErBa 3B 9O 18Powder melts in crucible, and temperature of fusion is 1037 ℃-1042 ℃, and melt heat up is surpassed about temperature of fusion 30-50 ℃ and be incubated 0.5-2 days, guarantees that melt melts fully;
2) then melt temperature is reduced near the zero pour temperature of fusion of mixture (be 1037 ℃-1042 ℃) of melt, with 0.01-0.2 ℃/hour speed the temperature of melt is reduced about 1.5-3.0 ℃, has solidified for several millimeters inside from bath surface to melt like this, lowered the temperature 4-8 hour with 3-6 ℃/hour speed then, abundant with the partial crystallization of guaranteeing to solidify, last speed with 30-50 ℃/hour cools to room temperature, obtains ErBa 3B 9O 18Crystal.
Wherein, described solid state reaction step comprises according to stoichiometric ratio raw materials weighing Er 2O 3, BaCO 3And H 3BO 3, mix the back and under 920-960 ℃, carried out solid state reaction 24-36 hour.
Wherein, the purity of described raw material is 99.99%.
ErBa of the present invention 3B 9O 18Crystal has good optical, machinery and heat conductivility, higher chemical stability, and be easy to growth.This crystal can be used as the operation material of solid statelaser, particularly is used in the making of thin-sheet laser, and can be exported Solid State Laser by photoflash lamp, semiconductor laser or other light sources pumping.
Description of drawings
Below in conjunction with drawings and Examples the present invention is done description further: wherein,
Accompanying drawing 1 is ErBa 3B 9O 18Crystal monocrystalline X ray diffracting spectrum;
Accompanying drawing 2 is ErBa 3B 9O 18Crystal;
Accompanying drawing 3 is ErBa 3B 9O 18The crystalline x-ray diffractogram of powder;
Accompanying drawing 4 is ErBa 3B 9O 18The crystalline absorption spectrum;
Accompanying drawing 5 is ErBa 3B 9O 18The crystalline emmission spectrum.
Embodiment
Embodiment 1:ErBa 3B 9O 18The crystalline Czochralski grown
Take by weighing the Er of 143.3g 2O 3, 444.0g BaCO 3With 417.0g H 3BO 3, raw material is put into agate mortar fully grind, evenly mixed.The platinum crucible that raw material is housed is put into box retort furnace post-heating to 930-960 ℃, be incubated 32 hours and carry out solid state reaction, middle available agate mortar grinds 3 times to react fully.Slow then cool to room temperature can obtain pure ErBa 3B 9O 18The powder phase.Crucible is put into monocrystal growing furnace the inside, and raw material is warmed up to above about 40 ℃ of fusing points (1040 ℃), promptly about 1080 ℃, and, guarantee that melt melts fully this temperature insulation 20 hours.Then melt temperature is reduced near 1039 ℃ the zero pour (also being 1040 ℃ of fusing points) of melt, with platinum wire contact melt and with 2-5 ℃ of 0.1-0.3 ℃/hour speed cooling, can obtains some seed crystals then.With the seed crystal that the platinum chuck on the seed rod fixedly obtains, the insulation of 1cm place is 15 minutes above melt, introduces seed crystal then in melt, and with 0.05 ℃/hour speed cooling, pulling rate is 0.05mm/h, and speed of rotation is 20rpm, can obtain ErBa 3B 9O 18Crystal.Fig. 1 is ErBa 3B 9O 18Crystalline monocrystalline X ray diffracting spectrum with document [X.Z.Li, C.Wang, X.L.Chen, H.Li, L.S.Jia, L.Wu, Y.X.Du, and Y.P.Xu, Inorg.Chem., 2004 (43): 8555-8560.] contrast, can show that this crystal really is ErBa 3B 9O 18Crystal.
Embodiment 2:ErBa 3B 9O 18The growth of crystalline slow cooling method
Take by weighing the Er of 95.5g 2O 3, 296.0g BaCO 3With 278.0g H 3BO 3, raw material is put into agate mortar fully grind, evenly mixed.The platinum crucible that raw material is housed is put into box retort furnace post-heating to 930-960 ℃, be incubated 24-36 hour and carry out solid state reaction, middle available agate mortar grinds 2-3 time to react fully.Slow then cool to room temperature can obtain pure ErBa 3B 9O 18The powder phase is loose rose pink meal.Crucible is put into monocrystal growing furnace the inside, and raw material is warmed up to above about 30 ℃ of fusing points (1040 ℃), promptly about 1070 ℃, and, guarantee that melt melts fully this temperature insulation 1 day.Then melt temperature is reduced near 1039 ℃ the zero pour (also being 1040 ℃ of fusing points) of melt, lower the temperature about a week with 0.01 ℃/hour speed then, the temperature of melt has approximately been fallen 2 ℃ like this, and inner some millimeters have solidified from bath surface to melt, lowered the temperature 6 hours with 5 ℃/hour speed then, abundant to guarantee solidifying partial crystallization.Last speed with 50 ℃/hour cools to room temperature, can obtain ErBa shown in Figure 2 3B 9O 18Crystal, this monocrystalline size is 15 * 20 * 5mm 3Then crystal is carried out the x ray powder diffraction, its collection of illustrative plates is shown among Fig. 3, can know crystalline crystalline structure data behind indexing, and it is a hexagonal system, and spacer is P6 3/ m, unit cell parameters is a=b=7.17～7.19 ; C=16.98～17.00 .This crystal has good optical, machinery and heat conductivility, higher chemical stability, not deliquescence and be easy to the growth.
Application Example 1:ErBa 3B 9O 18The measurement of crystal absorption spectrum
We utilize the ErBa of non-polarized light to a polishing both surfaces 3B 9O 18Crystal has carried out the test of absorption spectrum.About 1 millimeter of crystalline thickness.Fig. 3 is this crystalline abosrption spectrogram.As seen from Figure 4, the ABSORPTION EDGE of crystalline short wavelength one end is about 200nm.The 200nm of test be positioned in the 1700nm scope 255,376,407,485,519,650,971 and the absorption peak of 1540nm corresponding to Er 3+From 4I 15/2Arrive 4D 7/2, 4G 11/2, 2H 11/2, 4F 7/2, 4H 11/2, 4F 9/2, 4I 11/2With 4I 13/2The transition of each energy level.The absorption peak at 1540nm place is very strong, illustrates that corresponding transition probability is very big, and this strong emission for this wave band provides a kind of possibility.
Application Example 2:ErBa 3B 9O 18The measurement of crystal emission spectrum
With wavelength is the laser excitation ErBa of 532nm 3B 9O 18Crystal at the range of receiving of 500-1700nm, has been found stronger fluorescent emission at the 1540nm place.Fig. 5 is ErBa 3B 9O 18Crystalline fluorescence spectrum figure.From emission spectrum as can be seen, the shape of spectral line and absorption spectrum are very approaching, and the several main emission peak that emission band comprised is also corresponding with absorption spectrum, and Er is described 3+Though the concentration quenching phenomenon does not take place ionic concentration very high (form with a kind of component exists), this helps improving the luminous efficiency of laser crystals.
It should be noted that to be that example is to ErBa provided by the present invention only herein with the gentle cold process of crystal pulling method 3B 9O 18The crystalline melt method for growing is illustrated, but to what those skilled in the art may be obvious that is, the boratory melt growth method of any routine all can be carried out this crystalline growth.Equally, on the technical solution of the present invention basis, also can carry out variations and modifications, but not break away from the generalized scope of the present invention's claims required for protection technical scheme of the present invention.

Claims (12)

1, a kind of ErBa 3B 9O 18Laser crystals, it is a hexagonal system, spacer P6 3/ m, unit cell parameters is a=b=7.17～7.19 ; C=16.98～17.00 .
2, laser crystals as claimed in claim 1 is characterized in that, described ErBa 3B 9O 18Crystal is a monocrystalline.
3, laser crystals as claimed in claim 2 is characterized in that, described crystalline size is not less than 1 * 1 * 0.5mm 3
4, as each described laser crystals of claim 1-3, it is characterized in that described ErBa 3B 9O 18Laser crystals is easy to processing, water insoluble and deliquescence not.
5, as each described ErBa of claim 1-4 3B 9O 18The preparation method of laser crystals, wherein this method adopts conventional melting method to carry out the crystalline growth.
6, preparation method as claimed in claim 5 is characterized in that, the melting method of described routine comprises crystal pulling method, slow cooling method or warm terraced method.
7, preparation method as claimed in claim 6, wherein, described Czochralski grown ErBa 3B 9O 18Laser crystals specifically may further comprise the steps:
1) with solid state reaction synthetic ErBa 3B 9O 18Powder melts in crucible, and temperature of fusion is 1037 ℃-1042 ℃, and melt is heated up above temperature of fusion 30-50 ℃, keeps 0.5-2.0 days, rolls back 1037 ℃-1042 ℃ after melt fully melts;
2) seed crystal can obtain by utilizing platinum wire contact melt and slowly lowering the temperature;
3) following seed crystal makes seed crystal 0.5-2.0cm place preheating 10-30 minute above melt, makes seed crystal contact melt then;
4) carry out isodiametric growth then, wherein pulling rate is 0.02-1.0mm/h, and rotating speed is 10-50rpm;
5) growth is slowly cooled off after reaching desired size, obtains ErBa 3B 9O 18Laser crystals.
8, preparation method as claimed in claim 6, wherein said slow cooling method growth ErBa 3B 9O 18Laser crystals specifically may further comprise the steps:
1) with solid state reaction synthetic ErBa 3B 9O 18Powder melts in crucible, and temperature of fusion is 1037 ℃-1042 ℃, and melt heat up is surpassed temperature of fusion 30-50 ℃ and be incubated 0.5-2.0 days, guarantees that melt melts fully;
2) then melt temperature is reduced to the zero pour of melt, and the temperature of melt is reduced 1.5-3.0 ℃ with 0.01-0.2 ℃/hour speed, has solidified for several millimeters inside from bath surface to melt like this, lowered the temperature 4-8 hour with 3-6 ℃/hour speed then, abundant with the partial crystallization of guaranteeing to solidify, last speed with 30-50 ℃/hour cools to room temperature, obtains ErBa 3B 9O 18Crystal.
As claim 7 or 8 described preparation methods, it is characterized in that 9, the step of described solid state reaction comprises according to stoichiometric ratio raw materials weighing Er 2O 3, BaCO 3And H 3BO 3, mix the back and under 920-960 ℃, carried out solid state reaction 24-36 hour.
10, as each described ErBa of claim 1-4 3B 9O 18The purposes of laser crystals, described crystal can be used for the operation material of solid statelaser.
11, ErBa as claimed in claim 10 3B 9O 18The purposes of laser crystals is characterized in that, described crystal can be used for the operation material of thin slice solid statelaser.
12, ErBa as claimed in claim 10 3B 9O 18The purposes of laser crystals is characterized in that, described crystal can be exported Solid State Laser, Er wherein by photoflash lamp, semiconductor laser or other light sources pumping 3+Ion sends its characteristic fluorescence as luminescence center.
CN 200710098764 2007-04-26 2007-04-26 Laser crystal ErBa3B9O18 of borate, preparation method, and usage Pending CN101092745A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200710098764 CN101092745A (en) 2007-04-26 2007-04-26 Laser crystal ErBa3B9O18 of borate, preparation method, and usage

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200710098764 CN101092745A (en) 2007-04-26 2007-04-26 Laser crystal ErBa3B9O18 of borate, preparation method, and usage

Publications (1)

Publication Number Publication Date
CN101092745A true CN101092745A (en) 2007-12-26

Family

ID=38991176

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200710098764 Pending CN101092745A (en) 2007-04-26 2007-04-26 Laser crystal ErBa3B9O18 of borate, preparation method, and usage

Country Status (1)

Country Link
CN (1) CN101092745A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101519273B (en) * 2009-04-13 2011-10-05 中国科学院物理研究所 Serial rare-earth borate laser glass and preparation method and purpose of same
CN107400927A (en) * 2017-08-10 2017-11-28 中国科学院福建物质结构研究所 A kind of crystalline material, its preparation method and application

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101519273B (en) * 2009-04-13 2011-10-05 中国科学院物理研究所 Serial rare-earth borate laser glass and preparation method and purpose of same
CN107400927A (en) * 2017-08-10 2017-11-28 中国科学院福建物质结构研究所 A kind of crystalline material, its preparation method and application
CN107400927B (en) * 2017-08-10 2019-10-29 中国科学院福建物质结构研究所 A kind of crystalline material, preparation method and application

Similar Documents

Publication Publication Date Title
CN101476156B (en) Gadolinium, yttrium, scandium and gallium doped garnet, gadolinium-yttrium-scandium-gallium-aluminum garnet and crystal growth method by melt method
WO2010009581A1 (en) A doped low temperature phase barium metaborate single crystal, growth method and frequency converter thereof
CN102946048A (en) Raman laser based on crystalline in fresnoite structure
CN106676635B (en) Tellurate crystal and its growth process and application
CN102534777A (en) Neodymium-doped potassium gadolinium phosphate laser crystal, and preparation method and application thereof
CN102766905B (en) Erbium ion activated 1.55 micron waveband gallate laser crystalss and preparation method thereof
CN101092745A (en) Laser crystal ErBa3B9O18 of borate, preparation method, and usage
CN102618928A (en) High-efficiency mid-infrared laser crystal and preparation method thereof
CN101037804A (en) Yttrium erbium ion gadolinium sodium molybdate double-doped laser crystal and preparation method and usage thereof
CN105154975A (en) Near-1.33-mu-mu-wavelength thermally-bonded composite laser crystal and preparation method thereof
CN102766906A (en) Erbium ion activated 3-micron wave-band gallate laser crystal and its preparation method
CN1837419B (en) Ytterbium doped Y0.8LaCa4O(BO3)3 laser crystal, its preparation method and use
CN102337591B (en) Ytterbium-doped potassium triyttrium borate laser crystal, and growing method and application thereof
CN111101198B (en) Neodymium-doped zinc bismuth borate self-frequency-doubling crystal material, cut type, preparation method and application thereof
CN101469450A (en) Series erbium-ytterbium borate laser crystal Er1-xYbxBa3B9O18 (0<x<1), and preparation and use thereof
CN101319396A (en) Yb-doped yttrium lithium tungstate of femtosecond pulse laser crystal and preparation method thereof
CN101037802A (en) Yttrium neodymium gadolinium barium molybdate doped laser crystal and preparation method and usage thereof
CN103696007A (en) Nd, Er:GSAG laser crystal and its preparing method
CN100365172C (en) Yb-Er-codoped gadolinium silicate laser crystal and preparation method thereof
CN101717998A (en) Neodymium-doped silicic acid yttrium lutetium laser crystal and preparation method thereof
CN105603524A (en) Yttrium phosphate series laser crystal, preparation method and uses thereof
Jubera et al. Crystal growth and optical characterizations of Yb3+-doped LiGd 6 O 5 (BO 3) 3 single crystal: a new promising laser material
CN112522786A (en) Self-excited Raman composite functional crystal bismuth tungsten molybdate and crystal growth method thereof
CN101709507A (en) Neodymium-doped silicic acid yttrium gadolinium laser crystal and preparation method thereof
CN102978705A (en) Thulium and holmium co-doped gadolinium lithium molybdate laser crystal, and preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20071226