CN101514489B - Fluoborate containing rare earth ions, crystal, growth method and application of crystal - Google Patents
Fluoborate containing rare earth ions, crystal, growth method and application of crystal Download PDFInfo
- Publication number
- CN101514489B CN101514489B CN2008101008310A CN200810100831A CN101514489B CN 101514489 B CN101514489 B CN 101514489B CN 2008101008310 A CN2008101008310 A CN 2008101008310A CN 200810100831 A CN200810100831 A CN 200810100831A CN 101514489 B CN101514489 B CN 101514489B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- crystal
- fluoroborate
- earth ion
- laser
- 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.)
- Expired - Fee Related
Links
- 239000013078 crystal Substances 0.000 title claims abstract description 120
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 14
- -1 rare earth ions Chemical class 0.000 title abstract description 49
- 230000003287 optical effect Effects 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 7
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 4
- 238000007716 flux method Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000004611 spectroscopical analysis Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 230000003203 everyday effect Effects 0.000 description 7
- 239000000155 melt Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 2
- 229910013641 LiNbO 3 Inorganic materials 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101100355584 Mus musculus Rad51 gene Proteins 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Lasers (AREA)
Abstract
The invention relates to a fluoborate containing rare earth ions, a crystal and a preparation method, and the chemical formula is as follows: 1-xRex)5(BO3)3F1-5xO5xWherein x is more than 0 and less than 0.2, Re3+Is Sc3+、Y3+Or a rare earth ion; rare earth ion is La3+、Ce3+、Pr3+、Nd3+、Sm3+，Eu3+、Gd3+、Tb3+、Dy3+、Ho3+、Er3+、Tm3+、Yb3+、Lu3+Or a mixture of rare earth ions; growing a rare earth-containing fluoborate crystal with high quality and larger size by adopting a fluxing agent method; the crystal is suitable for the requirement of frequency conversion of blue-green light wave band laser; the monocrystal doped with rare earth laser active ions can be used for manufacturing laser nonlinear optical composite functional devices; the laser made of the crystal can be used in the fields of spectroscopy, biomedicine, military affairs 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 practical application, 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 hope 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 Jonson 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 at present mixes Nd
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 difficult growth 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 also do not appear in the newspapers 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; Said 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 said rare earth ion; Said 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; Said 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 said rare earth ion; Said 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 purpose more 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 following:
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;
Said 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 said 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;
Said 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 said 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 following:
1) inserts in the crucible after will containing fluoroborate compound and the fusing assistant proportional mixing of rare earth ion; 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 mixed melt of the fluoroborate and the fusing assistant of rare earth ion;
The seed crystal that 2) will be contained on the seed rod is introduced above-mentioned steps 1) mixed melt surface or mixed melt among; Speed rotary seed crystal rod with 0-50rpm is cooled to the saturation point temperature, lowers 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 that is not more than 100 ℃/h;
Said fusing assistant is B
2O
3-Li
2O-CaF
2-LiF;
Saidly 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;
Said 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 said rare earth ion.
The said fluoroborate compound that contains rare earth ion is formed by containing Ca ion, rare earth ion, B ion and F ionic oxide compound, carbonate, halogenide, nitrate salt, 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 through at least one this produce the device that a branch of at least frequency is different from incident electromagnetic wave after containing the fluoroborate non-linear optic crystal of rare earth ion.
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 said 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 of boracic is used H
3BO
3Substitute, fluorochemicals is CaF
2The time be example, concrete chemical equation is following:
(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, it is laser diode-pumped to be fit to very much employing AlGaAs; Through obtaining the blue light about 404nm from frequency multiplication; Working as laser output wavelength in addition is 1064nm, equally also can be through obtain the green glow of 532nm from frequency multiplication; The laser apparatus of processing with this crystal can be used for numerous areas such as spectroscopy, biomedicine and military affairs.
Description of drawings
Accompanying drawing 1 is an instance 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, put into retort furnace (adding electrothermal stove) to crucible, 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 17.81g CaCO
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, put into retort furnace (adding electrothermal stove) to crucible, 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
3, mixed grinding is even, in retort furnace, melts under 1000 ℃ in Φ 60 * 60mm platinum crucible, and crucible is put into crystal growing furnace (homemade wire spiral process furnace); Be rapidly heated 1000 ℃, stirred 1 day, fast cooling to 800 ℃; Introduce seed crystal, make seed crystal at the following 0.5cm of melt liquid level, the seed rod SR is 30rpm; With 0.5 ℃ speed cooling every day (temperature controlling instruments is an Al-708P automatic temperature control instrument able to programme), grew for 2 weeks, treat that crystal growth finishes after; 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
3, mixed grinding is even, in retort furnace, melts under 1000 ℃ in Φ 70 * 70mm platinum crucible, and crucible is put into crystal growing furnace, is rapidly heated 1000 ℃; Stirred 2 days, fast cooling to 805 ℃ is introduced seed crystal, makes the seed crystal contact at bath surface; The seed rod SR is 30rpm, and pull rate is 1mm/h, with 0.2 ℃ speed cooling every day, growth 1-2 week; 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
0.96Nd
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
3, mixed grinding is even, in retort furnace, melts under 1000 ℃ in Φ 70 * 70mm platinum crucible, and crucible is put into crystal growing furnace (homemade wire spiral process furnace); Be rapidly heated 1000 ℃, stirred 2 days, fast cooling to 803 ℃; Introduce seed crystal, make seed crystal at the following 0.5cm of melt liquid level, the seed rod SR is 30rpm; With 0.3 ℃ speed cooling every day (temperature controlling instruments is an Al-708P automatic temperature control instrument able to programme), grew for 2 weeks, treat that crystal growth finishes after; 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)
3, mixed grinding is even, in retort furnace, melts under 1050 ℃ in Φ 60 * 50mm platinum crucible, and crucible is put into crystal growing furnace (homemade wire spiral process furnace); Be rapidly heated 1000 ℃, stirred 1 day, fast cooling to 795 ℃; Introduce seed crystal, make seed crystal at the following 0.5cm of melt liquid level, the seed rod SR is 30rpm; With 0.5 ℃ speed cooling every day (temperature controlling instruments is an Al-708P automatic temperature control instrument able to programme), grew for 2 weeks, treat that crystal growth finishes after; 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 170.1g CaCO
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 SR is 30rpm, and pull rate is 1mm/h, with 0.3 ℃ speed cooling every day, growth 1-2 week; 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
0.9Gd
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, in retort furnace, melts under 1000 ℃ in Φ 60 * 60mm platinum crucible, and crucible is put into crystal growing furnace; Be rapidly heated 1000 ℃, stirred 1 day, fast cooling to 794 ℃ is introduced seed crystal; Make seed crystal at the following 0.5cm of melt liquid level, the seed rod SR 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
3, mixed grinding is even, in retort furnace, melts under 1000 ℃ in Φ 60 * 60mm platinum crucible, and crucible is put into crystal growing furnace; Be rapidly heated 1000 ℃, stirred 1 day, fast cooling to 800 ℃ is introduced seed crystal; Seed crystal is just contacted at bath surface, and the seed rod SR 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, obtain (Ca with 40 ℃ speed annealing per hour
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 processed 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 supply the alternate rare earth ion to have variety.
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 (6)
1. a 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 at least a in the following ion: 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+
2. 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 at least a in the following ion: 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+
3. the described growth method that contains the fluoroborate non-linear optic crystal of rare earth ion of claim 2 is characterized in that, adopts the case of flux methods growth, and its step is following:
1) inserts in the crucible after will containing fluoroborate compound and the fusing assistant proportional mixing of rare earth ion; 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 mixed melt of the fluoroborate and the fusing assistant of rare earth ion;
The seed crystal that 2) will be contained on the seed rod is introduced above-mentioned steps 1) mixed melt surface or mixed melt among; Speed rotary seed crystal rod with 0-50rpm is cooled to the saturation point temperature, lowers 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 with the rate of temperature fall that is not more than 100 ℃/h;
Said fusing assistant is B
2O
3-Li
2O-CaF
2-LiF;
Saidly 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 at least a in the following ion: 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+
4. one kind 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 through at least one this produce the device that a branch of at least frequency is different from incident electromagnetic wave after containing the fluoroborate non-linear optic crystal of rare earth ion.
5. one kind 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,, 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.
6. one kind by the described purposes that contains the fluoroborate non-linear optic crystal of rare earth ion of claim 2, it is characterized in that, the said 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101008310A CN101514489B (en) | 2008-02-22 | 2008-02-22 | Fluoborate containing rare earth ions, crystal, growth method and application of crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101008310A CN101514489B (en) | 2008-02-22 | 2008-02-22 | Fluoborate containing rare earth ions, crystal, growth method and application of crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101514489A CN101514489A (en) | 2009-08-26 |
| CN101514489B true CN101514489B (en) | 2012-03-07 |
Family
ID=41039103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101008310A Expired - Fee Related CN101514489B (en) | 2008-02-22 | 2008-02-22 | Fluoborate containing rare earth ions, crystal, growth method and application of crystal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101514489B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140347B (en) * | 2010-01-28 | 2014-05-07 | 海洋王照明科技股份有限公司 | Borofluoride white light emitting material and preparation method thereof |
| CN102167972B (en) * | 2010-02-25 | 2013-11-27 | 海洋王照明科技股份有限公司 | Green halogen-doped calcium borate luminescent material and preparation method thereof |
| CN102071464B (en) * | 2011-01-21 | 2012-06-20 | 西北大学 | Nonlinear optical crystal material Sr3Y3BiB4O15 and preparation method and application thereof |
| CN102061513A (en) * | 2011-01-27 | 2011-05-18 | 中国科学院上海硅酸盐研究所 | Method for preparing large size calcium-rare earth borate crystal |
| US8873596B2 (en) * | 2011-07-22 | 2014-10-28 | Kla-Tencor Corporation | Laser with high quality, stable output beam, and long life high conversion efficiency non-linear crystal |
| CN108018606A (en) * | 2016-11-04 | 2018-05-11 | 中国科学院理化技术研究所 | RbZn2BO3Cl2Nonlinear optical crystal and preparation method and application thereof |
| CN110591703A (en) * | 2019-09-04 | 2019-12-20 | 湖北大学 | Preparation method of Sm-doped fluoborate red fluorescent powder |
| CN111139069A (en) * | 2020-01-07 | 2020-05-12 | 湖北大学 | Preparation method of rare earth Sm doped barium fluoborate red fluorescent powder |
| CN112144119B (en) * | 2020-08-19 | 2022-04-01 | 中国科学院福建物质结构研究所 | Rare earth doped barium calcium fluoborate laser crystal, preparation method thereof and method for realizing laser |
| CN115231824B (en) * | 2021-04-22 | 2023-12-01 | 天津工业大学 | Rare earth element Tm doped fluoborate luminescent glass and preparation method thereof |
| CN113818078B (en) * | 2021-09-22 | 2023-05-26 | 天津理工大学 | Europium-doped borate laser crystal material and preparation method and application thereof |
| CN116288713A (en) * | 2023-03-24 | 2023-06-23 | 天津理工大学 | Series fluorine-containing rare earth borate compound, fluorine-containing rare earth borate nonlinear optical crystal, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0693581B1 (en) * | 1994-07-18 | 1998-05-06 | Research Development Corporation Of Japan | A caesium-lithium-borate crystal and its application to frequency conversion of laser light |
| CN1236027A (en) * | 1998-05-14 | 1999-11-24 | 中国科学技术大学 | Compound R2MB10O10 as non-linear optical crystal and its preparation and use |
| US6083319A (en) * | 1995-02-21 | 2000-07-04 | Crismatec | Non-linear crystals and their applications |
| CN1712576A (en) * | 2004-06-25 | 2005-12-28 | 中国科学院理化技术研究所 | Cesium rubidium borate nonlinear optical crystal and growing method and application thereof |
| CN1727527A (en) * | 2004-07-30 | 2006-02-01 | 中国科学院理化技术研究所 | Boron aluminate, boron aluminate nonlinear optical crystal, and growth method and application thereof |
| CN1904148A (en) * | 2005-07-29 | 2007-01-31 | 中国科学院理化技术研究所 | Beryllium fluoroborate nonlinear optical crystal, and growing method and application thereof |
-
2008
- 2008-02-22 CN CN2008101008310A patent/CN101514489B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0693581B1 (en) * | 1994-07-18 | 1998-05-06 | Research Development Corporation Of Japan | A caesium-lithium-borate crystal and its application to frequency conversion of laser light |
| US6083319A (en) * | 1995-02-21 | 2000-07-04 | Crismatec | Non-linear crystals and their applications |
| CN1236027A (en) * | 1998-05-14 | 1999-11-24 | 中国科学技术大学 | Compound R2MB10O10 as non-linear optical crystal and its preparation and use |
| US6146553A (en) * | 1998-05-14 | 2000-11-14 | University Of Science And Technology Of China | Nonlinear optical crystal of compound R2 MB10 O19 and producing method and producing method and uses thereof |
| CN1712576A (en) * | 2004-06-25 | 2005-12-28 | 中国科学院理化技术研究所 | Cesium rubidium borate nonlinear optical crystal and growing method and application thereof |
| CN1727527A (en) * | 2004-07-30 | 2006-02-01 | 中国科学院理化技术研究所 | Boron aluminate, boron aluminate nonlinear optical crystal, and growth method and application thereof |
| CN1904148A (en) * | 2005-07-29 | 2007-01-31 | 中国科学院理化技术研究所 | Beryllium fluoroborate nonlinear optical crystal, and growing method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101514489A (en) | 2009-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101514489B (en) | Fluoborate containing rare earth ions, crystal, growth method and application of crystal | |
| CN101545138B (en) | Non-linear optical crystal-sodium beryllate borate, growth method and application thereof | |
| CN105668577B (en) | K3Ba3Li2Al4B6O20F compounds, K3Ba3Li2Al4B6O20F nonlinear optical crystals and its preparation method and purposes | |
| CN107021462A (en) | Selenium gallium zinc barium compound, selenium gallium zinc barium infrared nonlinear optical crystal and its production and use | |
| CN107699948B (en) | Serial composition metal RE borate and composition metal RE borate nonlinear optical crystal and preparation method and purposes | |
| CN106544731A (en) | Lead chlorate infrared nonlinear optical crystal and preparation method and purposes | |
| CN100523311C (en) | Crystal of barium tellurium aluminate, preparation method and application | |
| CN102352533B (en) | Nonlinear optical crystal boric acid beryllium sodium caesium | |
| CN104178812B (en) | The preparation method of vanadium potassium phosphate nonlinear optical crystal and purposes | |
| CN103088423A (en) | Compound barium boron oxyfluoride, barium boron oxyfluoride nonlinear optical crystal, and preparation methods and applications thereof | |
| CN101037796A (en) | Neodymium boracic acid oxygen calcium gadolinium lanthanum doped laser crystal and preparation method and usage thereof | |
| CN103451730B (en) | Cd 4 RO (BO 3) 3 compound, Cd 4 RO (BO 3) 3 optical crystal, preparation method and application | |
| CN102071464B (en) | Nonlinear optical crystal material Sr3Y3BiB4O15 and preparation method and application thereof | |
| CN106868588A (en) | Rb3Ba3Li2Al4B6O20F compounds, nonlinear optical crystal and its preparation method and purposes | |
| CN105839185A (en) | Cs2LiPO4 compound and Cs2LiPO4 nonlinear optical crystal as well as preparation method and application thereof | |
| WO2004007352A2 (en) | Borate crystals for optical frequency conversion | |
| Yoon | Crystal growth of the oxide fiber single crystal for optical applications | |
| CN109137073A (en) | A kind of lithium phosphate caesium yttrium nonlinear optical crystal and the preparation method and application thereof | |
| CN1122732C (en) | Magnesium zinc borophosphate nonlinear optical crystal and preparation method and application thereof | |
| CN100410428C (en) | Self frequency-conversion laser crystal rare earth ion activated rare earth molybdenate | |
| CN102260911A (en) | Novel nonlinear optical crystal medium temperature-phase potassium beryllium borate | |
| CN106868589A (en) | K3Sr3Li2Al4B6O20F compounds, nonlinear optical crystal and its preparation method and purposes | |
| CN103031602A (en) | Nonlinear optical crystal potassium calcium carbonate fluoride | |
| CN102260912A (en) | Novel nonlinear optical crystal low-temperature phase kalium beryllium borate | |
| CN102260913B (en) | Nonlinear optical crystal rubidium beryllium borate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120307 Termination date: 20130222 |