CN101514489A - Fluoborate and crystal containing rare earth ions, growing method and application of crystal - Google Patents
Fluoborate and crystal containing rare earth ions, growing method and application of crystal Download PDFInfo
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- CN101514489A CN101514489A CNA2008101008310A CN200810100831A CN101514489A CN 101514489 A CN101514489 A CN 101514489A CN A2008101008310 A CNA2008101008310 A CN A2008101008310A CN 200810100831 A CN200810100831 A CN 200810100831A CN 101514489 A CN101514489 A CN 101514489A
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Abstract
The invention relates to fluoborate and a crystal containing rare earth ions, and preparation method thereof. The chemical formula of the fluoborate is (Ca1-xRex)5(BO3)3F1-5xO5x, wherein x is more than 0 and less than 0.2; Re<3+> is Sc<3+>, Y<3+> or the rare earth ions; and the rare earth ions are La<3+>, Ce<3+>, Pr<3+>, Nd<3+>, Sm <3+>, Eu<3+>, Gd<3+>, Tb<3+>, Dy<3+>, Ho<3+>, Er<3+>, Tm<3+>, Yb<3+>, or Lu<3+>, or mixture of the rare earth ions. A flux method is adopted to grow a fluoborate crystal with high quality and large size; the crystal meets the requirement of blue green light wave-band laser frequency conversion, and can be used for manufacturing nonlinear optical devices; a monocrystal doped with rare-earth laser activated ions can manufacture laser-nonlinear multi-functional optical devices; and lasers manufactured by the crystal can be used in the fields such as spectroscopy, biomedicine, military, and the like.
Description
Technical field
The present invention relates to artificial lens and field of crystal growth in the optoelectronic function technical field, particularly a kind of fluoroborate, crystal and crystalline growth method and purposes that contains rare earth ion.
Background technology
Along with the development of laser technology, in actual applications different wavelength of laser all there is demand.And frequency multiplication is exactly a kind of method that changes the laser beam output wavelength that often is applied in the laser technology.It adopts a special non-linear optic crystal usually, places the laser beam front to change the laser beam output wavelength.The non-linear optical crystal material that is applied to the blue green light wave band at present mainly contains KTP (KTiOPO
4), BBO (BaB
2O
4) and LBO (LiB
3O
5) crystal etc.
In addition, people wish to obtain to have the crystalline material of complex function for a long time, can be combined with each other laser activity and frequency doubling property is self-frequency doubling laser crystal, to reduce loss, improve the working efficiency of laser apparatus, self-frequency doubling laser crystal is an ideal material of making the compact laser apparatus of mini-efficiently thus.The sixties in 20th century, people such as U.S. BELL laboratory Johnson are at LiNbO
3Mix active ions Tm in the crystal
3+, successfully grow Tm
3+: LiNbO
3Crystal has been realized the self-frequency-doubling laser running first, thereby has opened the prelude of laser self frequency-doubling crystal's research.The laser self frequency-doubling crystal who uses mixes Nd at present
3+And Yb
3+ReAl
3(BO
3)
4And ReCa
4O (BO
3)
3(Re is Gd and Y) series, but because a series of problems such as flux volatilization exist problems such as growth difficulty and crystal mass.
At present, the non-linear optic crystal of fluoroborate mainly contains CBF (Ca
5(BO
3)
3F), KBBF (MBe
2BO
3F
2, M is Li, Na, K, Rb, Cs) series, BCBF (BaCaBO
3F) and BABF (BaAlBO
3F
2).Up to now, the fluoroborate (Ca that contains rare earth
1-xRe
x)
5(BO
3)
3F
1-5xO
5x(0＜x＜0.2) with and yet there are no report as the application of non-linear optic crystal.
Summary of the invention
The object of the present invention is to provide a kind of fluoroborate that contains rare earth; Its chemical formula is: (Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x, 0＜x＜0.2 wherein, Re
3+Be Sc
3+, Y
3+, rare earth ion or laser active rare earth ion; Described rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+Or the mixing of described rare earth ion; Described laser active rare earth ion is Nd
3+, Pr
3+, Sm
3+, Eu
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+Or Yb
3+
Another object of the present invention is to provide a kind of fluoroborate non-linear optic crystal that contains rare earth; Its chemical formula is: (Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x, 0＜x＜0.2 wherein, Re
3+Be Sc
3+, Y
3+, rare earth ion or laser active rare earth ion; Described rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+Or the mixing of described rare earth ion; Described laser active rare earth ion is Nd
3+, Pr
3+, Sm
3+, Eu
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+Or Yb
3+This fluoroborate non-linear optic crystal has non-linear optical effect or has the laser and the non-linear complex optics effect that can produce self-frequency-doubling laser; Can be used for making device for non-linear optical, and can be used for producing the laser output of blue-greenish colour wave band.
A further object of the present invention provides a kind of growth method that contains the fluoroborate non-linear optic crystal of rare earth, and this method can be easier to (the Ca of growing high-quality, large-size
1-xRe
x)
5(BO
3)
3F
1-5xO
5xCrystal.
A further object of the invention just provides a kind of purposes of fluoroborate non-linear optic crystal, and this fluoroborate non-linear optic crystal has non-linear optical effect or has the laser and the non-linear complex optics effect that can produce self-frequency-doubling laser; Can be used for making device for non-linear optical, and can be used for producing the laser output of blue-greenish colour wave band.
Technical scheme of the present invention is as follows:
The fluoroborate compound that contains rare earth ion provided by the invention, its chemical formula is:
(Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x, 0＜x＜0.2 wherein, Re
3+Be Sc
3+, Y
3+Or rare earth ion;
Described rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+Or the mixing of described rare earth ion;
The fluoroborate non-linear optic crystal that contains rare earth ion provided by the invention, this fluoroborate non-linear optic crystal that contains rare earth ion belongs to oblique system, spacer is Cm, has non-linear optical effect or has non-linear optical effect and the complex optics effect that can produce the laser of self-frequency-doubling laser; This fluoroborate crystalline chemical formula that contains rare earth ion is: (Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x, 0＜x＜0.2 wherein, Re
3+Be Sc
3+, Y
3+Or rare earth ion;
Described rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+Or the mixing of described rare earth ion.
The growth method that contains the fluoroborate non-linear optic crystal of rare earth ion provided by the invention adopts the case of flux methods growth, and its step is as follows:
1) will contain and insert in the crucible after the fluoroborate compound of rare earth ion and fusing assistant are mixed in proportion, 10-30 ℃/hour temperature rise rate is heated 950-1050 ℃, constant temperature 10-40 hour, be cooled to the above 5-10 of saturation point temperature ℃ again, obtain containing the blend melt of the fluoroborate and the fusing assistant of rare earth ion;
2) seed crystal that will be contained on the seed rod is introduced above-mentioned steps 1) the blend melt surface or blend melt among, speed rotary seed crystal rod with 0-50rpm, be cooled to the saturation point temperature, lower the temperature with 0.2-1 ℃/day speed then, treat that single crystal growing is behind desired size, make this crystal break away from bath surface, and be annealed to room temperature, make the fluoroborate non-linear optic crystal that contains rare earth ion of the present invention with the rate of temperature fall of little 100 ℃/h;
Described fusing assistant is B
2O
3-Li
2O-CaF
2-LiF;
Describedly contain the fluoroborate compound of rare earth ion and the mole proportioning between each component of fusing assistant is:
(Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x∶B
2O
3∶Li
2O∶CaF
2∶LiF＝1∶0.5-1∶0-2∶0-1∶6-10；
The prepared chemical formula that contains the fluoroborate non-linear optic crystal of rare earth ion is: (Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x, 0＜x＜0.2 wherein, Re
3+Be Sc
3+, Y
3+Or rare earth ion;
Described rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+Or the mixing of described rare earth ion.
The described fluoroborate compound of rare earth ion that contains is by containing Ca ion, rare earth ion, B ion and F ionic oxide compound, carbonate, halogenide, nitrate, oxalate or borate.
The purposes that contains the fluoroborate non-linear optic crystal of rare earth ion provided by the invention, be, this fluoroborate non-linear optic crystal that contains rare earth ion is used for device for non-linear optical, this device for non-linear optical comprise with a branch of at least incident electromagnetic wave by at least one this contain and produce a branch of at least frequency behind the fluoroborate non-linear optic crystal of rare earth ion and be different from incident electromagnetic wave.
This fluoroborate non-linear optic crystal that contains rare earth ion is used for laser nonlinear optics multiple device, places in the optical resonator,, produce the laser output that fundamental frequency light and a branch of at least frequency are different from fundamental frequency light through the optical pumping effect.
The described fluoroborate non-linear optic crystal that contains rare earth ion is used to produce the laser apparatus of 406nm blue light and the output of 532nm green glow.
With the compound that contains Ca is CaCO
3, the oxide compound H of boracic
3BO
3Substitute, fluorochemicals is CaF
2The time be example, concrete chemical equation is as follows:
(9-5x) CaCO
3+ 5xRe
2O
3+ 6H
3BO
3+ (1-5x) CaF
2→ 2 (Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x+ (9-5x) CO
2+ 9H
2O, the x value is 0-0.2, Re
2O
3Amount add as required.
The fluoroborate non-linear optic crystal that contains rare earth ion of present method see through spectrum, absorption spectrum, fluorescence spectrum and fluorescence lifetime etc. are analyzed test shows, this crystal has strong absorption band near 808nm, be fit to very much adopt AlGaAs laser diode-pumped; By can obtain the blue light about 404nm from frequency multiplication; Working as laser output wavelength in addition is 1064nm, equally also can be by obtain the green glow of 532nm from frequency multiplication; The laser apparatus made from this crystal can be used for numerous areas such as spectroscopy, biomedicine and military affairs.
Description of drawings
Accompanying drawing 1 is an example that contains the fluoroborate non-linear optic crystal purposes of rare earth ion of the present invention, promptly is used to produce the synoptic diagram of frequency multiplication or self-frequency-doubling laser output;
Laser apparatus 1 first speculum 2 second speculums 3
Half-wave plate 4 first set of lenses 5 first set of lenses 6
Non-linear optic crystal 7 dispersing prisms 8
Embodiment
Embodiment 1: prepare Powdered (Ca
0.84Sc
0.16)
5(BO
3)
3F
0.2O
0.8Compound.
With 15.88g CaCO
3, 2.21gSc
2O
3, 7.42gH
3BO
3And 0.31gCaF
2After mixing, in the platinum crucible of Φ 40 * 40mm opening of packing into, crucible is put into retort furnace (adding electrothermal stove), 1100 ℃ of constant temperature made it sintering in 48 hours, obtained (Ca after the grinding
0.84Sc
0.16)
5(BO
3)
3F
0.2O
0.8Compound.
Embodiment 2: prepare Powdered (Ca
0.98Nd
0.02)
5(BO
3)
3F
0.9O
0.1Compound.
With 17.81gCaCO
3, 0.67gNd
2O
3, 7.42gH
3BO
3And 1.41gCaF
2After mixing, in the platinum crucible of Φ 40 * 40 openings of packing into, crucible is put into retort furnace (adding electrothermal stove), 1050 ℃ of constant temperature made it sintering in 72 hours, obtained (Ca after the grinding
0.98Nd
0.02)
5(BO
3)
3F
0.9O
0.1Compound powder, compound (Ca
0.98Nd
0.02)
5(BO
3)
3F
0.9O
0.1Has luminescent properties.
Embodiment 3: adopt B
2O
3-Li
2O-CaF
2-LiF fusing assistant kyropoulos growth (Ca
0.96Y
0.04)
5(BO
3)
3F
0.8O
0.2Crystal.
With 72.24gCaO, 65.14gH
3BO
3, 17.57gCaF
2, 22.87gLi
2CO
3, 110.25gLiF14.75gY
2O
3Mixed grinding is even, in retort furnace, melt under 1000 ℃ in Φ 60 * 60mm platinum crucible, crucible is put into crystal growing furnace (homemade resistance wire process furnace), be rapidly heated 1000 ℃, stirred 1 day, fast cooling to 800 ℃ is introduced seed crystal, make seed crystal at the following 0.5cm of melt liquid level, the seed rod speed of rotation is 30rpm, with 0.5 ℃ speed cooling every day (temperature controlling instruments is an Al-708P automatic temperature control instrument able to programme), grows for 2 weeks, after treating that crystal growth finishes, crystal is lifted from bath surface, be cooled to room temperature, obtain (Ca with 40 ℃ speed annealing per hour
0.96Y
0.04)
5(BO
3)
3F
0.8O
0.2Monocrystalline, this crystal has non-linear optical effect.
Embodiment 4: adopt B
2O
3-Li
2O-CaF
2-LiF flux pulling technique growth (Ca
0.96Nd
0.04)
5(BO
3)
3F
0.8O
0.2The self-frequency-doubling crystal.
With 129.11gCaCO
3, 44.22gB
2O
3, 35.08gCaF
2, 11.41g Li
2CO
3, 121.54gLiF and 21.97gNd
2O
3Mixed grinding is even, in retort furnace, melt under 1000 ℃ in Φ 70 * 70mm platinum crucible, crucible is put into crystal growing furnace, be rapidly heated 1000 ℃, stirred 2 days, fast cooling to 805 ℃, introduce seed crystal, make the seed crystal contact at bath surface, the seed rod speed of rotation is 30rpm, and pull rate is 1mm/h, with 0.2 ℃ speed cooling every day, growth 1-2 week, treat that crystal growth finishes after, crystal is lifted from bath surface, be cooled to room temperature with 40 ℃ speed annealing per hour, obtain (Ca
0.96Nd
0.04)
5(BO
3)
3F
0.8O
0.2Monocrystalline.This crystal is the laser self frequency-doubling crystal, can be used as the non-linear composite functional material of laser.
Embodiment 5: adopt B
2O
3-Li
2O-CaF
2-LiF fusing assistant, kyropoulos growth (Ca
0.92Yb
0.08)
5(BO
3)
3F
0.6O
0.4The self-frequency-doubling crystal.
With 158.74gCaC
2O
4, 47.39gB
2O
3, 35.08gCaF
2, 12.43g Li
2CO
3, 108.01gLiF and 51.48gYb
2O
3Mixed grinding is even, in retort furnace, melt under 1000 ℃ in Φ 70 * 70mm platinum crucible, crucible is put into crystal growing furnace (homemade resistance wire process furnace), be rapidly heated 1000 ℃, stirred 2 days, fast cooling to 803 ℃ is introduced seed crystal, make seed crystal at the following 0.5cm of melt liquid level, the seed rod speed of rotation is 30rpm, with 0.3 ℃ speed cooling every day (temperature controlling instruments is an Al-708P automatic temperature control instrument able to programme), grows for 2 weeks, after treating that crystal growth finishes, crystal is lifted from bath surface, be cooled to room temperature, obtain (Ca with 30 ℃ speed annealing per hour
0.92Yb
0.08)
5(BO
3)
3F
0.6O
0.4Monocrystalline.This crystal is the laser self frequency-doubling crystal, can be used as the non-linear composite functional material of laser.
Embodiment 6: adopt B
2O
3-Li
2The O-LiF fusing assistant, kyropoulos growth (Ca
0.98Tm
0.02)
5(BO
3)
3F
0.9O
0.1The self-frequency-doubling crystal.
With 132.11gCaCO
3, 80.58gH
3BO
3, 11.08gLi
2CO
3, 90.24gLiF and 23.18gTm (NO
3)
3Mixed grinding is even, in retort furnace, melt under 1050 ℃ in Φ 60 * 50mm platinum crucible, crucible is put into crystal growing furnace (homemade resistance wire process furnace), be rapidly heated 1000 ℃, stirred 1 day, fast cooling to 795 ℃ is introduced seed crystal, make seed crystal at the following 0.5cm of melt liquid level, the seed rod speed of rotation is 30rpm, with 0.5 ℃ speed cooling every day (temperature controlling instruments is an Al-708P automatic temperature control instrument able to programme), grows for 2 weeks, after treating that crystal growth finishes, crystal is lifted from bath surface, be cooled to room temperature, obtain (Ca with 30 ℃ speed annealing per hour
0.98Tm
0.02)
5(BO
3)
3F
0.9O
0.1Monocrystalline, this crystal is the laser self frequency-doubling crystal, can be used as the non-linear composite functional material of laser.
Embodiment 7: top-seeded solution growth growth (Ca
0.9Gd
0.1)
5(BO
3)
3F
0.5O
0.5Frequency-doubling crystal.
With 170.1gCaCO
3, 100.24gH
3BO
317.56gCaF
2, 18.56g Li
2CO
3, 120.41gLiF and 24.35gGd
2O
3, after mixing, in the platinum crucible of Φ 70 * 70mm opening of packing into, crucible is put into crystal growing furnace, be rapidly heated 1040 ℃, stirred 1 day, fast cooling to 810 ℃ is introduced seed crystal, and seed crystal is just contacted at bath surface, the seed rod speed of rotation is 30rpm, and pull rate is 1mm/h, with 0.3 ℃ speed cooling every day, growth 1-2 week, treat that crystal growth finishes after, crystal is lifted from bath surface, be cooled to room temperature with 40 ℃ speed annealing per hour, obtain (Ca
0.9Gd
0.1)
5(BO
3)
3F
0.5O
0.5Frequency-doubling crystal.
Embodiment 8: kyropoulos growth (Ca
0.96Yb
0.02Er
0.02)
5(BO
3)
3F
0.8O
0.2Two laser self frequency-doubling crystals that mix.
With 129.11gCaCO
3, 65.14gH
3BO
3, 17.57gCaF
2, 22.87gLi
2CO
3, 110.25gLiF, 12.49gEr
2O
3And 12.87gYb
2O
3, mixed grinding is even, melts under 1000 ℃ in retort furnace in Φ 60 * 60mm platinum crucible, crucible is put into crystal growing furnace, be rapidly heated 1000 ℃, stirred 1 day, fast cooling to 794 ℃ is introduced seed crystal, makes seed crystal at the following 0.5cm of melt liquid level, the seed rod speed of rotation is 30rpm, with 0.5 ℃ speed cooling every day, grows for 2 weeks, after treating that crystal growth finishes, crystal is lifted from bath surface, be cooled to room temperature, obtain (Ca with 40 ℃ speed annealing per hour
0.96Yb
0.02Er
0.02)
5(BO
3)
3F
0.8O
0.2Two laser self frequency-doubling crystals that mix.
Embodiment 9: top seed crystal Czochralski grown (Ca
0.96Eu
0.02Er
0.02)
5(BO
3)
3F
0.8O
0.2Two laser self frequency-doubling crystals that mix.
With 129.11gCaCO
3, 65.14gH
3BO
3, 17.57gCaF
2, 22.87gLi
2CO
3, 110.25gLiF, 11.57gEu
2O
3And 12.49gEr
2O
3Mixed grinding is even, in retort furnace, melt under 1000 ℃ in Φ 60 * 60mm platinum crucible, crucible is put into crystal growing furnace, be rapidly heated 1000 ℃, stirred 1 day, fast cooling to 800 ℃, introduce seed crystal, seed crystal is just contacted at bath surface, and the seed rod speed of rotation is 30rpm, and pull rate is 1mm/h, with 0.3 ℃ speed cooling every day, growth 1-2 week, treat that crystal growth finishes after, crystal is lifted from bath surface, be cooled to room temperature with 40 ℃ speed annealing per hour, obtain (Ca
0.96Eu
0.02Er
0.02)
5(BO
3)
3F
0.8O
0.2Two laser self frequency-doubling crystals that mix.
Embodiment 10: with (Ca
0.96La
0.04)
5(BO
3)
3F
0.8O
0.2Crystal is made the frequency doubling device that produces green glow output
(the Ca that embodiment 3 is grown
0.96Y
0.04)
5(BO
3)
3F
0.8O
0.2Crystal is made into frequency doubling device, is installed in 7 position by shown in the accompanying drawing 1, and at room temperature, with transferring Q Nd:YAG laser apparatus as light source, incident wavelength is the infrared light of 1064nm, and output wavelength is the green laser of 532nm.Among Fig. 1,1 is laser apparatus, and 2 is first speculum, and 3 is second speculum, and 4 is half-wave plate, and 5 is first set of lenses, and 6 is first set of lenses, and 7 are the fluoroborate non-linear optic crystal that contains rare earth ion of the present invention, and 8 is dispersing prism.
The fluoroborate non-linear optic crystal that contains rare earth ion of the present invention has not deliquescence, and physical and chemical performance is stable, and can have diversity for the alternate rare earth ion.
Embodiment 11:
(the Ca that embodiment 4 is grown
0.98Ho
0.02)
5(BO
3)
3F
0.9O
0.1Laser self-frequency-doubling's device that crystal is made into places the optical resonator of being made up of total reflective mirror and outgoing mirror, and is laser diode-pumped with AlGaAs, can obtain to export from frequency doubling Blue-light.
Claims (7)
1, a kind of fluoroborate compound that contains rare earth ion is characterized in that, this chemical formula that contains the fluoroborate compound of rare earth ion is: (Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x, 0＜x＜0.2 wherein, Re
3+Be Sc
3+, Y
3+Or rare earth ion;
Described rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+Or the mixing of described rare earth ion.
2, a kind of fluoroborate non-linear optic crystal that contains rare earth ion, it is characterized in that, this fluoroborate non-linear optic crystal that contains rare earth ion belongs to oblique system, spacer is Cm, has non-linear optical effect or has non-linear optical effect and the complex optics effect that can produce the laser of self-frequency-doubling laser; This fluoroborate crystalline chemical formula that contains rare earth ion is: (Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x, 0＜x＜0.2 wherein, Re
3+Be Sc
3+, Y
3+Or rare earth ion;
Described rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+Or the mixing of described rare earth ion.
3, the described growth method that contains the fluoroborate non-linear optic crystal of rare earth ion of a kind of claim 2 is characterized in that, adopts the case of flux methods growth, and its step is as follows:
1) will contain and insert in the crucible after the fluoroborate compound of rare earth ion and fusing assistant are mixed in proportion, 10-30 ℃/hour temperature rise rate is heated 950-1050 ℃, constant temperature 10-40 hour, be cooled to the above 5-10 of saturation point temperature ℃ again, obtain containing the blend melt of the fluoroborate and the fusing assistant of rare earth ion;
2) seed crystal that will be contained on the seed rod is introduced above-mentioned steps 1) the blend melt surface or blend melt among, speed rotary seed crystal rod with 0-50rpm, be cooled to the saturation point temperature, lower the temperature with 0.2-1 ℃/day speed then, treat that single crystal growing is behind desired size, make this crystal break away from bath surface, and be annealed to room temperature, make the fluoroborate non-linear optic crystal that contains rare earth ion of the present invention with the rate of temperature fall of little 100 ℃/h;
Described fusing assistant is B
2O
3-Li
2O-CaF
2-LiF;
Describedly contain the fluoroborate compound of rare earth ion and the mole proportioning between each component of fusing assistant is:
(Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x∶B
2O
3∶Li
2O∶CaF
2∶LiF＝1∶0.5-1∶0-2∶0-1∶6-10；
The prepared chemical formula that contains the fluoroborate non-linear optic crystal of rare earth ion is: (Ca
1-xRe
x)
5(BO
3)
3F
1-5xO
5x, 0＜x＜0.2 wherein, Re
3+Be Sc
3+, Y
3+Or rare earth ion;
Described rare earth ion is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+, Lu
3+Or the mixing of described rare earth ion.
4, by the described growth method that contains the fluoroborate non-linear optic crystal of rare earth ion of claim 3, it is characterized in that the described fluoroborate compound of rare earth ion that contains is by containing Ca ion, rare earth ion, B ion and F ionic oxide compound, carbonate, halogenide, nitrate, oxalate or borate.
5, a kind of by the described purposes that contains the fluoroborate non-linear optic crystal of rare earth ion of claim 2, it is characterized in that, this fluoroborate non-linear optic crystal that contains rare earth ion is used for device for non-linear optical, this device for non-linear optical comprise with a branch of at least incident electromagnetic wave by at least one this contain and produce a branch of at least frequency behind the fluoroborate non-linear optic crystal of rare earth ion and be different from incident electromagnetic wave.
6, a kind of by the described purposes that contains the fluoroborate non-linear optic crystal of rare earth ion of claim 2, it is characterized in that, this fluoroborate non-linear optic crystal that contains rare earth ion is used for laser nonlinear optics multiple device, place in the optical resonator, through the optical pumping effect, produce the laser output that fundamental frequency light and a branch of at least frequency are different from fundamental frequency light.
7, a kind ofly it is characterized in that the described fluoroborate non-linear optic crystal that contains rare earth ion is used to produce the laser apparatus of 406nm blue light and the output of 532nm green glow by the described purposes that contains the fluoroborate non-linear optic crystal of rare earth ion of claim 2.
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