CN103451730B - Cd4rO (BO3)3compound, Cd4rO (BO3)3optical crystal and preparation method and purposes - Google Patents
Cd4rO (BO3)3compound, Cd4rO (BO3)3optical crystal and preparation method and purposes Download PDFInfo
- Publication number
- CN103451730B CN103451730B CN201210184173.4A CN201210184173A CN103451730B CN 103451730 B CN103451730 B CN 103451730B CN 201210184173 A CN201210184173 A CN 201210184173A CN 103451730 B CN103451730 B CN 103451730B
- Authority
- CN
- China
- Prior art keywords
- crystal
- laser
- temperature
- compound
- nonlinear
- 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
Abstract
The present invention relates to Cd4RO(BO3)3Compound, Cd4RO(BO3)3Optical crystal and preparation method and purposes, be nonlinear optical crystal when R one in Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or at least two；It is a kind of for Nd when these at least two kinds of elements have3+, Pr3+, Sm3+, Eu3+, Dy3+, Ho3+, Er3+, Tm3+Or/and Yb3+Laser active dopant ion；And doping content is Laser-Nonlinear optics multifunctional crystal when being 0.01 10.0wt%；All use CdO B2O3Flux growth metrhod grows；Having nonlinear optical effect, good mechanical property, not deliquescence, be suitable for blue green light wave band of laser frequency conversion, can be used for making device for non-linear optical, rare earth doped laser-active ions crystal can make Laser-Nonlinear optics composite function device.
Description
Technical field
The present invention relates to chemical formula is Cd4RO(BO3)3(R is selected from Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, the one of Tm, Yb, Lu or at least two element) compound, its nonlinear optical crystal, the preparation method of this crystal and utilize the device for non-linear optical and Laser-Nonlinear optics composite function device that this crystal makes.
Technical background
The crystal with nonlinear optical effect is referred to as nonlinear optical crystal.Here nonlinear optical crystal effect refers to the effect such as frequency multiplication and frequency, difference frequency, parameter amplification.The crystal the most without symmetrical centre has been only possible to nonlinear optical effect.Utilize the nonlinear optical effect of crystal, the device for non-linear optical such as second harmonic generator, upper and lower frequency converter, optical parametric oscillator can be made.The laser that laser instrument produces can carry out frequency conversion by device for non-linear optical, thus obtains the laser of more useful wavelength, makes laser instrument be more widely used.All solid state bluish-green laser system can be carried out frequency conversion through nonlinear optical crystal again by solid state laser generation near-infrared laser and realize, and has huge application prospect at laser technology field.
The nonlinear optical material being applied to all solid state bluish-green laser system at present mainly has KTP (KTiOPO4) (see USA Magazine " Journal of Applied Phisics ", Vol.47,4980,1976)、BBO(β-Ba2B2O4) (seeing " Chinese science " B28,235,1985) and LBO (LiB3O5) crystal (seeing " Chinese invention patent " 88102084).These materials have weak point in growth: owing to KTP and LBO is non-congruent compound, and BBO has phase transformation under fusing point, and they are required for using flux growth metrhod to grow, the speed of growth is slow, being difficult to obtain large-size crystals, cost is high, have impact on the large-scale application of all solid state laser.Rare earth nonlinear optical crystal is the crystalline material that a class is unique.Because rare earth ion has the biggest connected property on coordination structure, their physicochemical properties make rare earth ion when replacing (partly or entirely), be not result in the sudden change of crystal structure, thus easily realize the modification of material, it has been found that this kind of rare earth material have YAl3(BO3)3(seeing former Soviet Union's magazine " Kristal und Technik " Vol.9,63,1974), NdxY1-xAl3(BO3)4(seeing " China's Physics Letters " Vol.3,413,1986), CaMO (BO3)3(M=La, Gd, Sm, Er, Y, Lu) (seeing USA Magazine " Chemistry Material " Vol.4,737,1992), R2MB10O19(R represents a kind of or at least two element, selected from rare earth element or Y;M is selected from Ca, Sr, Ba) (Chinese invention patent CN1084399C, United States Patent (USP) US6 are seen, 146,553) and Na3La9O3 (BO3) 8 (sees Chinese invention patent CN1142328C, United States Patent (USP) US6,921,498B2) etc., these crystal can be used to make blue green light wave band device for non-linear optical.
Present invention aim at providing a kind of Cd4RO(BO3)3Compound and preparation method, the one during wherein R is selected from Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or at least two element；
Another object of the present invention is to provide a kind of Cd4RO(BO3)3Nonlinear optical crystal and the preparation method of this crystal
Still a further object of the present invention is to provide a kind of Cd4RO(BO3)3Laser-Nonlinear optics multifunctional crystal and preparation method；
The present invention also has a mesh to be to provide a kind of Cd4RO(BO3)3Nonlinear optical crystal and Cd4RO(BO3)3The purposes of Laser-Nonlinear optics multifunctional crystal.
Technical scheme is as follows:
The Cd that the present invention provides4RO(BO3)3Compound, wherein R is the one in Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or at least two element.
The Cd that the present invention provides4RO(BO3)3The preparation method of compound, its preparation process is as follows: after containing R compound, ratio mix homogeneously containing Cd compound and boride alloy R:Cd:B=1:8:3 in molar ratio, carry out chemosynthesis reaction, prepares Cd4RO(BO3)3Compound；
Described is the oxide of R, the chloride of R, the carbonate of R, the nitrate of R or the oxalates of R containing R compound；Wherein, R is the one in Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or at least two element；
Described is the oxide of Cd, the chloride of Cd, the carbonate of Cd, the nitrate of Cd or the oxalates of Cd containing Cd compound；
Described boride alloy is H3BO3Or B2O3。
The Cd that the present invention provides4RO(BO3)3Nonlinear optical crystal, wherein R is the one in Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or at least two element, and this crystal does not have symmetrical centre, belongs to monoclinic system, and space group is Cm；This crystal has non-linear optical property.
The Cd that the present invention provides4RO(BO3)3The preparation method of nonlinear optical crystal, uses CdO-B2O3Flux system flux growth metrhod growth crystal, its step is as follows:
1) dispensing: by Cd4RO(BO3)3Compound and CdO-B2O3Cd pressed by flux4RO(BO3)3: CdO:B2O3For 1:1～4:1～8 molar ratio ingredients and carry out pretreatment；Or
Directly use according to R2O3:CdO:B2O3For the molar ratio ingredient of 1:10～16:5～19, and carry out pretreatment；
2) heat up: the platinum crucible filling above-mentioned dispensing is placed in crystal oven, is warming up to be completely melt, and at such a temperature constant temperature to the abundant homogenizing of high temperature solution；
3) seed crystal is introduced: by step 2) high temperature solution that obtains is down to above 0-10 DEG C of saturation temperature, the saturation temperature of crystal growth is found by seed crystal trial and error method, lentamente the seed crystal fixed is introduced in high temperature solution surface or high temperature solution above 5-25 DEG C of saturation temperature, after constant temperature 10-200 minute, it is cooled to rapidly saturation temperature；
4) control parameters and carry out crystal growth: in crystal growing process, using saturation temperature as the initial temperature of cooling, lower the temperature with the speed of 0-5 DEG C/day, simultaneously with speed rotating crystal and/or the crucible of 0-100rpm, carry out crystal growth；After crystal growth arrives required size, by crystal lift-off liquid level, it is down to room temperature with the speed less than 50 DEG C/h, obtains Cd4RO(BO3)3Crystal；
The pretreatment of described pretreated raw material is to pour in corundum crucible after the raw material mix homogeneously that will have configured, in Muffle furnace, it is to slowly warm up to 200 DEG C heat more than 10 hours, then heat to 500 DEG C heat more than 24 hours, product is fused in platinum crucible in batches, after be cooled to room temperature；
Described Cd4RO(BO3)3In compound, R is the one selected from Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or at least two element；
Described R2O3Replacing with the oxalates of the chloride of R, the carbonate of R, the nitrate of R or R, R is selected from the one in Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or at least two element；
The oxalates of the chloride of described CdO Cd, the carbonate of Cd, the nitrate of Cd or Cd replaces；
Described B2O3Use H3BO3Replace.
The Cd that the present invention provides4RO(BO3)3Laser-Nonlinear optics multifunctional crystal, described R is at least two element in Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and has a kind of for laser active dopant ion in these at least two kinds of elements；Described laser active dopant ion is Nd3+, Pr3+, Sm3+, Eu3+, Dy3+, Ho3+, Er3+, Tm3+Or Yb3+；The doping content of described laser active dopant ion is 0.01-10.0wt%.
The Cd that the present invention provides4RO(BO3)3The preparation method of Laser-Nonlinear optics multifunctional crystal, its preparation process is as follows:
1) Cd is prepared4RO(BO3)3Laser-Nonlinear optics complex function compound:
After containing R compound, ratio mix homogeneously containing Cd compound and boride alloy R:Cd:B=1:8:3 in molar ratio, carry out chemosynthesis reaction, prepare Cd4RO(BO3)3Compound；
Described is the oxide of R, the chloride of R, the carbonate of R, the nitrate of R or the oxalates of R containing R compound；Wherein, R is at least two element in Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and has a kind of for laser active dopant ion in these at least two kinds of elements；Described laser active dopant ion is Nd3+, Pr3+, Sm3+, Eu3+, Dy3+, Ho3+, Er3+, Tm3+Or Yb3+；Doping content 0.01-10.0wt% of described laser active dopant ion；
Described is the oxide of Cd, the chloride of Cd, the carbonate of Cd, the nitrate of Cd or the oxalates of Cd containing Cd compound；
Described boride alloy is H3BO3Or B2O3；
2) CdO-B is used2O3Flux growth metrhod growth Cd4RO(BO3)3Laser-Nonlinear optics multifunctional crystal, its step is as follows:
(1) dispensing: step 1) gained Cd4RO(BO3)3Laser-Nonlinear optics complex function compound and CdO-B2O3Cd pressed by flux4RO(BO3)3:CdO:B2O3For the molar ratio ingredient of 1:1～4:1～8, and carry out pretreatment；
(2) heat up: the platinum crucible filling above-mentioned dispensing is placed in crystal oven, is warming up to be completely melt, and at such a temperature constant temperature to the abundant homogenizing of high temperature solution；
(3) seed crystal is introduced: by step 2) pyrosol that obtains is down to above 0-10 DEG C of saturation temperature, the saturation temperature of crystal growth is found by seed crystal trial and error method, lentamente the seed crystal fixed is introduced in pyrosol surface or pyrosol above 5-25 DEG C of saturation temperature, after constant temperature 10-200 minute, it is cooled to rapidly saturation temperature；
(4) control parameters and carry out crystal growth: in crystal growing process, using saturation temperature as the initial temperature of cooling, lower the temperature with the speed of 0～3 DEG C/day, simultaneously with 0～100rpm speed rotating crystal and/or crucible, carry out crystal growth；After crystal growth arrives required size, by crystal lift-off liquid level, it is down to room temperature with the speed less than 50 DEG C/h, obtains Cd4RO(BO3)3Laser-Nonlinear optics multifunctional crystal；
The pretreatment of described pretreated raw material is to pour in corundum crucible after the raw material mix homogeneously that will have configured, in Muffle furnace, it is to slowly warm up to 200 DEG C heat more than 10 hours, then heat to 500 DEG C heat more than 24 hours, product is fused in platinum crucible in batches, after be cooled to room temperature；
Described Cd4RO(BO3)3In compound, R is the one selected from Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or at least two element；
Described R2O3Replacing with the oxalates of the chloride of R, the carbonate of R, the nitrate of R or R, R is selected from the one in Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or at least two element；
The oxalates of the chloride of described CdO Cd, the carbonate of Cd, the nitrate of Cd or Cd replaces；
Described B2O3Use H3BO3Replace.
The Cd that the present invention provides4RO(BO3)3The purposes of nonlinear optical crystal, this crystal is used for device for non-linear optical, this device for non-linear optical comprises the most a branch of incidence electromagnetic radiation and produces, by after at least one block of nonlinear optical crystal, the device that the most a branch of frequency is different from the output radiation of incidence electromagnetic radiation, it is characterized in that, nonlinear optical crystal therein is Cd4RO(BO3)3Monocrystal.
The Cd that the present invention provides4RO(BO3)3The purposes of Laser-Nonlinear optics multifunctional crystal, it is characterized in that, this crystal is used for Laser-Nonlinear optics composite function device, it is placed in optical resonator, through optical pumping source effect, generation basic frequency laser and the most a branch of frequency are different from the laser output of fundamental frequency, it is characterised in that the Laser-Nonlinear optics multifunctional crystal in resonator cavity is the Cd doped with rare earth laser-active ions4RO(BO3)3Monocrystal.
The following is several typical available Cd4RO(BO3)3The chemical reaction of compound:
(1)8CdCO3+R2O3+3B2O3=Cd4RO(BO3)3+8CO2↑
(2)8Cd(NO3)2+R2O3+3B2O3=2Cd4RO(BO3)3+16NO2↑+4O2↑
(3)8CdC2O4+R2O3+3B2O3=2Cd4RO(BO3)3+8CO↑+8CO2↑
(4)8CdCO3+R2O3+6H3BO3=2Cd4RO(BO3)3+8CO2↑+9H2O↑
(5)8Cd(NO3)2+R2O3+6H3BO3=2Cd4RO(BO3)3+16NO2↑+4O2↑+9H2O↑
(6)8CdC2O4+R2O3+6H3BO3=2Cd4RO(BO3)3+8CO↑+8CO2↑+9H2O↑。
The Cd of the present invention4RO(BO3)3Nonlinear optical crystal, wherein R is selected from Y, the one of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or at least two element；This crystal does not have symmetrical centre, belongs to monoclinic system, Cm space group.
The Cd that the present invention carries4RO(BO3)3Laser-Nonlinear optics multifunctional crystal, wherein, R is at least two element in Y, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, and has a kind of for laser active dopant ion in these at least two kinds of elements；Described laser active dopant ion is Nd3+, Pr3+, Sm3+, Eu3+, Dy3+, Ho3+, Er3+, Tm3+Or Yb3+；The doping content of described laser active dopant ion is 0.01-10.0wt%；Cd4RO(BO3)3When having rare earth ion doped in Laser-Nonlinear optics multifunctional crystal, the trivalent ion owing to being adulterated has abundant energy level, can obtain the luminescence of multiple color, as luminescent material, has good application prospect.
Post processing and the optical manufacturing method of crystal are as follows: after crystal growth terminates, and make crystal depart from melt liquid level, will stay annealing in growth furnace by crystal, be down to room temperature with the speed of no more than 100 DEG C/hr, preferably rate of temperature fall 30-50 DEG C/hr;According to the crystallography data of crystal, crystal boule is oriented, according to required angle, thickness and sectional dimension sliced crystal, crystal is led to light mirror polish, can not only be used for device for non-linear optical and use.The optical manufacturing method of above-mentioned nonlinear optical crystal is content familiar to those skilled in the art.Crystal provided by the present invention to optical manufacturing precision without particular/special requirement.
It is an advantage of the current invention that: obtained crystal has wider through wave band, bigger powder SHG effect.Cd4RO(BO3)3It is stable that nonlinear optical crystal has physical and chemical performance, not deliquescence, it is easy to processing and preserve and be wide through scope, its UV-permeable cut-off limit is 315nm, powder SHG effect and LBO (LiB3O5) identical；Nonlinear optical crystal of the present invention can be used for making device for non-linear optical, and at room temperature, with Nd:YAG Q-switched laser as light source, incident wavelength is the infrared light of 1064nm, and output wavelength is the green laser of 532nm, laser intensity and LBO (LiB3O5) identical.
Cd4RO(BO3)3It is stable that Laser-Nonlinear optics multifunctional crystal has physical and chemical performance, not deliquescence, it is easy to processes and preserves and be wide through scope, easily obtains large-size monocrystal under existing flux system；Laser-Nonlinear optics multifunctional crystal of the present invention can be used for making laser self-frequency-doubling's optics, at room temperature, the optics that Laser-Nonlinear optics multifunctional crystal of the present invention is made is placed in the optical resonator being made up of total reflective mirror and outgoing mirror, pumping source is made with small-sized xenon flash lamp, iraser can be produced, and iraser is carried out frequency conversion by the nonlinear optical effect of available crystal itself, both iraser output can have been obtained, green self-frequency-doubling laser output, laser activity and the Nd:GdCa under equal conditions can be obtained again4O(BO3)3Quite.
Accompanying drawing explanation
Fig. 1 is Cd of the present invention4RO(BO3)3Nonlinear optical crystal is fabricated to the fundamental diagram schematic diagram of device for non-linear optical, wherein: 1 is laser instrument, and 2 is incoming laser beam, and 3 is the Cd through crystal post processing and optical manufacturing4RO(BO3)3Monocrystal, 4 is produced shoot laser bundle, and 5 is filter plate.
Fig. 2 is Cd of the present invention4GdO(BO3)3Polycrystal powder X ray diffracting spectrum.
Fig. 3 is the Cd of the present invention4GdO(BO3)3Crystal passes through collection of illustrative plates.
Fig. 4 is the Cd of the present invention4GdO(BO3)3Crystal structure figure.
Fig. 5 is the Cd of the present invention4(Gd0.96Nd0.04)O(BO3)3Crystal structure figure.
Detailed description of the invention
1 couple of present invention uses Cd below in conjunction with the accompanying drawings4RO(BO3)3The device for non-linear optical that crystal makes elaborates.Sent light beam 2 by laser instrument 1 and inject Cd4RO(BO3)3Monocrystal 3, produced outgoing beam 4 is by filter plate 5, thus the laser beam required for obtaining.This device for non-linear optical can make frequency multiplication generator, upper and lower frequency converter, optical parametric oscillator etc..Laser instrument 1 can use neodymium-doped yttrium-aluminum garnet (Nd:YAG) laser instrument or other laser instrument, to use Nd:YAG laser light source frequency doubling device for, incident beam 2 be wavelength be the infrared light of 1064nm, pass through Cd4RO(BO3)3Monocrystalline produces the green glow frequency doubled light that wavelength is 532nm, and outgoing beam 4 is containing infrared light and the green glow of 532nm that wavelength is 1064nm, and the effect of filter plate 5 is to filter off infrared light composition, only allows green frequency doubled light to pass through.
The Cd of the present invention4CdO(BO3)3Crystal is as the purposes of device for non-linear optical, being that this device for non-linear optical comprises the most a branch of incidence electromagnetic radiation by producing the device that the most a branch of frequency is different from the output radiation of incidence electromagnetic radiation after at least one block of nonlinear optical crystal, nonlinear optical crystal therein is Cd4RO(BO3)3Monocrystal.
For the present invention doped with the Cd of rare earth laser-active ions4RO(BO3)3Laser-Nonlinear optics multifunctional crystal, in addition to such use, it is also possible to making Laser-Nonlinear optics composite function device with it, this device is placed in optical resonator, encouraging through optical pumping source, generation fundamental frequency light and the most a branch of frequency are different from the laser output of fundamental frequency；It is characterized in that, the Laser-Nonlinear optics composite function device in resonator cavity is the Cd mixed with rare earth laser-active ions4RO(BO3)3Monocrystal.
A kind of concrete (Gd0.96Nd0.04) Cd4B3O10Crystal is as the purposes of the self-frequency-doubling laser device of one of Laser-Nonlinear optics composite function device, it is that this device is placed in the optical resonator being made up of total reflective mirror and outgoing mirror, encourage through optical pumping source, crystal produces iraser, and this infrared light is carried out frequency conversion by the nonlinear optical effect of available crystal itself, both can obtain the output of infrared basic frequency laser, and have and can obtain green double-frequency laser output；It is characterized in that, the self-frequency-doubling laser device in resonator cavity is (Gd0.96Nd0.04) Cd4B3O10Monocrystal.
The Cd of the present invention4RO(BO3)3Nonlinear optical crystal and Cd4RO(BO3)3Laser-Nonlinear optics multifunctional crystal: Cd4RO(BO3)3Nonlinear optical crystal has a bigger nonlinear optical effect, and good mechanical property is not easily broken, not deliquescence, it is easy to process and preserve；By Cd of the present invention4RO(BO3)3Nonlinear optical crystal is fabricated to interface dimensions 5x5mm, the device for non-linear optical of optical direction thickness 7mm, at room temperature, with adjusting Q Nd:YAG laser light source, incident wavelength is the infrared light of 1064nm, output wavelength is the green laser of 532nm, and laser intensity iraser as using irradiates identical with green laser intensity produced by size lbo crystal；
Cd4RO(BO3)3What Laser-Nonlinear optics multifunctional crystal can be made into is placed in the optical resonator being made up of total reflective mirror and outgoing mirror from frequency doubling device, encourages through optical pumping source, and crystal produces iraser output, can obtain again green double-frequency laser output.
In principle, the Cd that can obtain a size of Centimeter Level sent out by existing flux4RO(BO3)3Monocrystal；Use large scale crucible, then can obtain the monocrystal of corresponding large-size.
Embodiment 1: use solid reaction process to prepare powder Cd4GdO(BO3)3Compound.
Reaction equation is as follows: 8CdCO3+Gd2O3+3B2O3=Cd4GdO(BO3)3+8CO2↑；
Above-mentioned three kinds of reagent inventory: CdCO3: 68.97 grams (0.4mol)；Gd2O3: 18.13 grams (0.05mol)；B2O3: 10.45 grams (0.15mol).
Concrete operation step is: weigh reagent respectively by above-mentioned dosage, they is put in mortar, and mixing is also carefully ground, and is then charged intoIn the opening platinum crucible of 40mm × 30mm, it is compacted into, puts in Muffle furnace, with the ramp of 30 DEG C/h to 500 DEG C and constant temperature 24h, take out crucible after cooling, now sample is more loose, takes out sample and re-grinds uniformly, then is placed in crucible and compacting, 120h is sintered in 800 DEG C in Muffle furnace, midway is taken out and is ground 1～2 time, obtains product, and product XRD figure is composed as shown in Figure 2.
Use above-mentioned same procedure, by Gd2O3Replace with other rare earth oxides outside La or Y2O3, all can obtain corresponding Cd4RO(BO3)3Compound.
Embodiment 2: preparation powder Cd4(Gd0.96Nd0.04)O(BO3)3Compound.
By Cd (NO3)2: 94.574 grams；Gd2O3: 17.04 grams；Nd2O3: 0.68 gram, B2O3: 10.45 grams of mixing are also carefully ground, and are then charged intoIn the opening platinum crucible of 40mm × 30mm, it is compacted into, put in Muffle furnace, with the ramp of 30 DEG C/h to 500 DEG C and constant temperature 24h, take out crucible after cooling, now sample is more loose, take out sample to re-grind uniformly, then be placed in crucible and compacting, in Muffle furnace, sinter 120h in 800 DEG C, midway is taken out and is ground 1～2 time, obtains products C d4(Gd0.96Nd0.04)O(BO3)3Powder, compound Cd4(Gd0.96Nd0.04)O(BO3)3There is luminescent properties.
Embodiment 3: use flux growth metrhod to prepare Cd4(Gd0.96Nd0.04)O(BO3)3Crystal, with CdO-B2O3For flux；
Compound Cd by embodiment 2 gained4(Gd0.96Nd0.04)O(BO3)3Powder 319.52 grams, 102.72 grams CdO and 49.44 grams of H3BO3, i.e. mol ratio Cd4(Gd0.96Nd0.04)O(BO3)3∶CdO∶H3BO3It is 1: 2: 2, loadsIn the opening platinum crucible of 60mm × 60mm, pretreated crucible is put in vertical monocrystal growing furnace, with insulation material, the opening being positioned at furnace roof portion is sealed up, one is stayed to be available for the aperture that seed rod comes in and goes out in furnace roof portion with corresponding position, crucible center, it is rapidly heated 1080 DEG C, constant temperature 24h, makes the abundant homogenizing of high temperature solution, and the saturation temperature searching out crystal growth by seed crystal trial and error method is 1025 DEG C.Above-mentioned high temperature solution is cooled to 1035 DEG C (more than saturation temperature 10 DEG C), the Cd that will cut along b axle4(Gd0.96Nd0.04)O(BO3)3Seed crystal platinum wire is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible to be allowed to contact with melt liquid level, the rotary speed of seed rod is 30rpm, constant temperature 20 minutes, fast cooling to 1025 DEG C, then lower the temperature with the speed of 0.4 DEG C/day, after 10 days, crystal growth terminates, by crystal lift-off melt liquid level, anneal with the speed of 40 DEG C/hr and be cooled to room temperature, it is thus achieved that the Cd of a size of 7 × 6 × 6mm4(Gd0.96Nd0.04)O(BO3)3Monocrystalline.
Make in aforementioned manners by Gd2O3And Nd2O3Replace with other rare earth oxides outside La or Y2O3, all can obtain corresponding Cd4RO(BO3)3Monocrystalline.
Embodiment 4: use flux growth metrhod to prepare Cd4YbO(BO3)3Crystal, with CdO-B2O3For flux；
By 256.82 grams of CdO, 65.68 grams of Yb2O3With 185.50 grams of H2BO3, i.e. mol ratio is Yb2O3∶CdO∶H2BO3After uniformly mix at=1: 12: 18, loadIn the opening platinum crucible of 60mm × 60mm, pretreated crucible is put in vertical monocrystal growing furnace, with insulation material, the opening being positioned at furnace roof portion is sealed up, one is stayed to be available for the aperture that seed rod comes in and goes out in furnace roof portion with corresponding position, crucible center, it is rapidly heated 1030 DEG C, constant temperature 24h, makes the abundant homogenizing of high temperature solution, and the saturation temperature searching out crystal growth by seed crystal trial and error method is 984 DEG C.Above-mentioned high temperature solution is cooled to 995 DEG C (more than saturation temperature 11 DEG C), the Cd that will cut along b axle4YbO(BO3)3Seed crystal platinum wire is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible to be allowed to contact with melt liquid level, the rotary speed of seed rod is 30rpm, constant temperature 20 minutes, fast cooling to 984 DEG C, then lower the temperature with the speed of 0.3 DEG C/day, after 10 days, crystal growth terminates, by crystal lift-off melt liquid level, anneal with the speed of 40 DEG C/hr and be cooled to room temperature, it is thus achieved that the Cd of a size of 8 × 7 × 5mm4RO(BO3)3Monocrystalline.
Make in aforementioned manners by Yd2O3Replace with other rare earth oxides outside La or Y2O3, all can obtain corresponding Cd4RO(BO3)3Monocrystalline.
Embodiment 5: use flux growth metrhod to prepare Cd4GdO(BO3)3Crystal, with CdO-H3BO3For flux；
Weigh CdO 256.82 grams, Gd2O345.32 gram, H3BO3247.34 grams, i.e. mol ratio Gd2O3∶CdO∶H3BO3=1: 16: 32, after mix homogeneously, loadIn the opening platinum crucible of 60mm × 60mm, crucible through pretreatment is put in vertical monocrystal growing furnace, with insulation material, the opening being positioned at furnace roof portion is sealed up, one is stayed to be available for the aperture that seed rod comes in and goes out in furnace roof portion with corresponding position, crucible center, it is rapidly heated 1015 DEG C, constant temperature 24h, makes the abundant homogenizing of high temperature solution, and the saturation temperature searching out crystal growth by seed crystal trial and error method is 956 DEG C.Above-mentioned high temperature solution is cooled to 965 DEG C (more than saturation temperature 9 DEG C), the Cd that will cut along b axle4GdO(BO3)3Seed crystal platinum wire is fixed on seed rod lower end, from furnace roof portion aperture, seed crystal is imported crucible to be allowed to contact with melt liquid level, the rotary speed of seed rod is 30rpm, constant temperature 20 minutes, fast cooling to 956 DEG C, then lower the temperature with the speed of 0.4 DEG C/day, after 10 days, crystal growth terminates, by crystal lift-off melt liquid level, anneal with the speed of 40 DEG C/hr and be cooled to room temperature, it is thus achieved that the Cd of a size of 8 × 7 × 7mm4GdO(BO3)3Monocrystalline.
Make in aforementioned manners by Gd2O3Replace with other rare earth oxides outside La or Y2O3, all can obtain corresponding Cd4RO(BO3)3Monocrystalline.
Embodiment 6: by embodiment 5 gained Cd4GdO(BO3)3Nonlinear optical crystal is made through spectroscopic assay, as shown in Figure 3, this crystal is transparent in 315nm to 2500nm wave-length coverage, crystal is not easily broken, it is prone to cutting, polishing and preservation, not deliquescence, crystal is made sectional dimension 5x5mm, the frequency doubling device of printing opacity thickness 7mm, by accompanying drawing 1 shown device 3 position, at room temperature, with adjusting Q Nd:YAG laser instrument as light source, incident wavelength is the infrared light of 1064nm, output wavelength is 532nm green laser, green laser intensity produced by the lbo crystal of laser intensity iraser irradiation same size as using is identical.
Embodiment 7: by embodiment 3 gained Cd4(Gd0.96Nd0.04)O(BO3)3Crystal makes sectional dimension 4x4mm, the self-frequency-doubling laser device of printing opacity direction thickness 6mm, is placed in the optical resonator being made up of total reflective mirror and outgoing mirror, makees pumping source with small-sized xenon flash lamp, it is thus achieved that iraser and green self-frequency-doubling laser output.
Those of ordinary skill in the art uses similar method to be not difficult to use Cd4RO(BO3)3Crystal produces other device for non-linear optical, and as above, lower frequency transducer, optical parametric oscillator etc., these all can not be beyond spirit and scope of this invention.
Claims (6)
1. a Cd4RO(BO3)3Nonlinear optical crystal, it is characterised in that wherein R is selected from Ce, Pr, Nd,
A kind of element in Sm, Eu, Tb, Dy, Ho, Er and Tm, or be selected from Y, Ce, Pr, Nd, Sm, Eu,
At least two element in Tb, Dy, Ho, Er, Tm, Yb and Lu, this crystal does not have symmetrical centre, belongs to monocline
Crystallographic system, space group is Cm；This crystal has non-linear optical property.
2. Cd described in a claim 14RO(BO3)3The preparation method of nonlinear optical crystal, it is characterised in that
Use CdO-B2O3Flux system flux growth metrhod growth crystal, its step is as follows:
1) dispensing: by Cd4RO(BO3)3Compound and CdO-B2O3Cd pressed by flux4RO(BO3)3: CdO:B2O3For 1:1～
4:1～8 molar ratio ingredients also carry out pretreatment；Or
Directly use according to R2O3:CdO:B2O3For the molar ratio ingredient of 1:10～16:5～19, and carry out pretreatment；
2) heat up: the platinum crucible filling above-mentioned dispensing is placed in crystal oven, is warming up to be completely melt, and in this temperature
The lower constant temperature of degree is to the abundant homogenizing of high temperature solution；
3) seed crystal is introduced: by step 2) high temperature solution that obtains is down to above 0-10 DEG C of saturation temperature, tastes with seed crystal
Examination method finds the saturation temperature of crystal growth, is drawn by the seed crystal fixed lentamente above 5-25 DEG C of saturation temperature
Entering in high temperature solution surface or high temperature solution, constant temperature, after 10-200 minute, is cooled to rapidly saturation temperature；
4) control parameters and carry out crystal growth: in crystal growing process, using saturation temperature rising as cooling
Beginning temperature, lowers the temperature with the speed of 0-5 DEG C/day, simultaneously with speed rotating crystal and/or the crucible of 0-100rpm, enters
Row crystal growth；After crystal growth arrives required size, by crystal lift-off liquid level, with the speed less than 50 DEG C/h
Rate is down to room temperature, obtains Cd4RO(BO3)3Crystal；
The pretreatment of described dispensing is to pour in corundum crucible, in Muffle furnace after the raw material mix homogeneously that will have configured
It is to slowly warm up to 200 DEG C heat more than 10 hours, then heats to 500 DEG C and heat more than 24 hours, product is divided
Batch be fused in platinum crucible, after be cooled to room temperature；
Described Cd4RO(BO3)3In compound, R is selected from Y, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er,
The one of Tm, Yb and Lu or at least two element；
Described R2O3The oxalates that can also use the chloride of R, the carbonate of R, the nitrate of R or R replaces, R
One in Y, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb and Lu or at least two
Element；
Described CdO can also use the oxalates of the chloride of Cd, the carbonate of Cd, the nitrate of Cd or Cd to replace；
Described B2O3H can also be used3BO3Replace.
3. a Cd4RO(BO3)3Laser-Nonlinear optics multifunctional crystal, it is characterised in that described R is choosing
At least two element in Y, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb and Lu, and
And these at least two kinds of elements have a kind of for laser active dopant ion；Described laser active dopant ion is Nd3+,
Pr3+, Sm3+, Eu3+, Dy3+, Ho3+, Er3+, Tm3+Or Yb3+；The doping content of described laser active dopant ion is
0.01-10.0wt%.
4. Cd described in a claim 34RO(BO3)3The preparation method of Laser-Nonlinear optics multifunctional crystal,
Its preparation process is as follows:
1) Cd is prepared4RO(BO3)3Laser-Nonlinear optics complex function compound:
Ratio containing R compound, containing Cd compound and boride alloy R:Cd:B=1:8:3 in molar ratio is mixed
After closing uniformly, carry out chemosynthesis reaction, prepare Cd4RO(BO3)3Compound；
Described is the oxide of R, the chloride of R, the carbonate of R, the nitrate of R or the grass of R containing R compound
Hydrochlorate；Wherein, R is in Y, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb and Lu
At least two element, and these at least two kinds of elements have a kind of for laser active dopant ion；Described laser swashs
Dopant ion of living is Nd3+, Pr3+, Sm3+, Eu3+, Dy3+, Ho3+, Er3+, Tm3+Or Yb3+；Described laser active is mixed
Doping content 0.01-10.0wt% of heteroion；
Described containing Cd compound be the oxide of Cd, the chloride of Cd, the carbonate of Cd, the nitrate of Cd or
The oxalates of Cd；
Described boride alloy is H3BO3Or B2O3；
2) CdO-B is used2O3Flux growth metrhod growth Cd4RO(BO3)3Laser-Nonlinear optics multifunctional crystal, its step
Rapid as follows:
(1) dispensing: step 1) gained Cd4RO(BO3)3Laser-Nonlinear optics complex function compound and CdO-B2O3
Cd pressed by flux4RO(BO3)3:CdO:B2O3For the molar ratio ingredient of 1:1～4:1～8, and carry out pretreatment；
(2) heat up: the platinum crucible filling above-mentioned dispensing is placed in crystal oven, is warming up to be completely melt, and at this
At a temperature of constant temperature to the abundant homogenizing of high temperature solution；
(3) seed crystal is introduced: by step 2) pyrosol that obtains is down to above 0-10 DEG C of saturation temperature, uses seed crystal
Trial and error method finds the saturation temperature of crystal growth, at the above 5-25 DEG C of seed crystal that will fix lentamente of saturation temperature
Introducing in pyrosol surface or pyrosol, constant temperature, after 10-200 minute, is cooled to rapidly saturation temperature；
(4) control parameters and carry out crystal growth: in crystal growing process, using saturation temperature as cooling
Initial temperature, lowers the temperature with the speed of 0～3 DEG C/day, simultaneously with 0～100rpm speed rotating crystal and/or crucible,
Carry out crystal growth；After crystal growth arrives required size, by crystal lift-off liquid level, with less than 50 DEG C/h's
Speed is down to room temperature, obtains Cd4RO(BO3)3Laser-Nonlinear optics multifunctional crystal；
The pretreatment of described dispensing is to pour in corundum crucible, in Muffle furnace after the raw material mix homogeneously that will have configured
It is to slowly warm up to 200 DEG C heat more than 10 hours, then heats to 500 DEG C and heat more than 24 hours, product is divided
Batch be fused in platinum crucible, after be cooled to room temperature.
5. Cd in a claim 14RO(BO3)3The purposes of nonlinear optical crystal, is used for non-linear by this crystal
Optics, this device for non-linear optical comprises the most a branch of incidence electromagnetic radiation by least one piece of nonlinear optics
The device that the most a branch of frequency is different from the output radiation of incidence electromagnetic radiation is produced after crystal, it is characterised in that its
In nonlinear optical crystal be Cd4RO(BO3)3Monocrystal.
6. Cd described in a claim 34RO(BO3)3The purposes of Laser-Nonlinear optics multifunctional crystal, its feature
It is, this crystal is used for Laser-Nonlinear optics composite function device, is placed in optical resonator, make through optical pumping source
With, generation basic frequency laser and the most a branch of frequency are different from the laser output of fundamental frequency, it is characterised in that swashing in resonator cavity
Optical nonlinear optics multifunctional crystal is the Cd doped with rare earth laser-active ions4RO(BO3)3Monocrystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210184173.4A CN103451730B (en) | 2012-06-05 | 2012-06-05 | Cd4rO (BO3)3compound, Cd4rO (BO3)3optical crystal and preparation method and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210184173.4A CN103451730B (en) | 2012-06-05 | 2012-06-05 | Cd4rO (BO3)3compound, Cd4rO (BO3)3optical crystal and preparation method and purposes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103451730A CN103451730A (en) | 2013-12-18 |
| CN103451730B true CN103451730B (en) | 2016-11-23 |
Family
ID=49734548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210184173.4A Expired - Fee Related CN103451730B (en) | 2012-06-05 | 2012-06-05 | Cd4rO (BO3)3compound, Cd4rO (BO3)3optical crystal and preparation method and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103451730B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741217B (en) * | 2014-01-20 | 2016-08-24 | 中国科学院理化技术研究所 | Yttrium borate sodium, yttrium borate sodium nonlinear optical crystal and preparation method and purposes |
| CN106398696A (en) * | 2015-08-03 | 2017-02-15 | 温州大学 | Oxide-based red long-afterglow luminescent material and preparation method therefor |
| CN108004593B (en) * | 2017-11-22 | 2020-11-06 | 青岛大学 | Method for improving fluorescence output efficiency of erbium-ytterbium co-doped laser crystal |
| CN111555107B (en) * | 2020-05-15 | 2021-07-23 | 山东大学 | Ytterbium ion doped ABGS crystal and self-frequency-doubling ultrashort pulse laser |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775646A (en) * | 2010-02-08 | 2010-07-14 | 中国科学院理化技术研究所 | Na3M2(BO3)3 nonlinear optical crystal as well as preparation method and application |
| CN102031562A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院福建物质结构研究所 | Non-linear optical crystal bismuth cadmium borate |
| CN102660771A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Boric acid oxygen cadmium gadolinium as nonlinear optical crystal |
| CN102660772A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Nonlinear optics crystal boric acid of oxygen, cadmium and lutetium |
| CN102660774A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Boric acid oxygen cadmium ytterbium as nonlinear optical crystal |
| CN102660773A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Non-linear optical crystal boric acid cadmium yttrium oxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7179405B2 (en) * | 2002-10-01 | 2007-02-20 | The Regents Of The University Of California | Nonlinear optical crystal optimized for Ytterbium laser host wavelengths |
-
2012
- 2012-06-05 CN CN201210184173.4A patent/CN103451730B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031562A (en) * | 2009-09-28 | 2011-04-27 | 中国科学院福建物质结构研究所 | Non-linear optical crystal bismuth cadmium borate |
| CN101775646A (en) * | 2010-02-08 | 2010-07-14 | 中国科学院理化技术研究所 | Na3M2(BO3)3 nonlinear optical crystal as well as preparation method and application |
| CN102660771A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Boric acid oxygen cadmium gadolinium as nonlinear optical crystal |
| CN102660772A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Nonlinear optics crystal boric acid of oxygen, cadmium and lutetium |
| CN102660774A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Boric acid oxygen cadmium ytterbium as nonlinear optical crystal |
| CN102660773A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Non-linear optical crystal boric acid cadmium yttrium oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103451730A (en) | 2013-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101302647B (en) | Large size barium borate bismuth nonlinear optical crystal and preparation thereof | |
| CN102337586B (en) | Compound barium borofluoride nonlinear optical crystal as well as preparation method and purposes thereof | |
| CN101311370B (en) | Large-sized bismuth zinc borate nonlinear optical crystal, preparation method and use | |
| CN102976287B (en) | BaGa2GeSe6 compound, BaGa2GeSe6 non-linear optical crystal and their preparation methods and use | |
| CN101775646A (en) | Na3M2(BO3)3 nonlinear optical crystal as well as preparation method and application | |
| CN103950912B (en) | RbBa 2(PO 3) 5compound, RbBa 2(PO 3) 5non-linear optic crystal and method for making thereof and purposes | |
| CN103628136B (en) | Compound boron phosphoric acid rubidium is plumbous and boron phosphoric acid rubidium lead nonlinear optical crystal and preparation method and purposes | |
| CN105668577A (en) | K3Ba3Li2Al4B6O20F compound, K3Ba3Li2Al4B6O20F nonlinear optical crystal, preparation method and application thereof | |
| CN103741217A (en) | Sodium yttrium borate, sodium yttrium borate nonlinear optical crystal as well as preparation method and application of sodium yttrium borate nonlinear optical crystal | |
| CN103451730B (en) | Cd4rO (BO3)3compound, Cd4rO (BO3)3optical crystal and preparation method and purposes | |
| CN104556084A (en) | Rb3Al3B3O10F compound, Rb3Al3B3O10F nonlinear optical crystals as well as preparation method and use thereof | |
| CN103173860B (en) | K3YB6O12 compound, K3YB6O12 nonlinear optical crystal and preparation methods and applications thereof | |
| CN107699948A (en) | Serial composition metal RE borate and composition metal RE borate nonlinear optical crystal and preparation method and purposes | |
| CN101295119A (en) | Novel nonlinear optical crystal boric acid aluminum gallium bismuth | |
| CN103628138B (en) | Large-size block Calcium pyroborate oxygen terbium crystal and growth with application | |
| CN103014868B (en) | Nonlinear optical crystal tellurious molybdic acid cadmium and its preparation and use | |
| CN105332045A (en) | Compound Pb0.78Ba8.22B18O36, Pb0.78Ba8.22B18O36 nonlinear optical crystal, preparation methods and application | |
| CN107287659B (en) | Laser crystal and preparation method thereof | |
| CN104178812A (en) | Preparation method and application of vanadium potassium phosphate nonlinear optical crystal | |
| CN103088423A (en) | Compound barium boron oxyfluoride, barium boron oxyfluoride nonlinear optical crystal, and preparation methods and applications thereof | |
| CN110468445A (en) | Boric acid caesium barium nonlinear optical crystal and its preparation method and application | |
| CN105839185A (en) | Cs2LiPO4 compound and Cs2LiPO4 nonlinear optical crystal as well as preparation method and application thereof | |
| CN102337591B (en) | Ytterbium-doped potassium triyttrium borate laser crystal, and growing method and application thereof | |
| CN103030146B (en) | BaGa2SiSe6 compound, BaGa2SiSe6 nonlinear optical crystal and preparation method and application | |
| CN101974783A (en) | Compound cesium lithium borate (CLBO) nonlinear optical crystal, 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161123 |