CN103046113A - Compound lead borate and nonlinear optical crystal of lead borate, preparation method thereof and purpose thereof - Google Patents

Compound lead borate and nonlinear optical crystal of lead borate, preparation method thereof and purpose thereof Download PDF

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CN103046113A
CN103046113A CN2011103064158A CN201110306415A CN103046113A CN 103046113 A CN103046113 A CN 103046113A CN 2011103064158 A CN2011103064158 A CN 2011103064158A CN 201110306415 A CN201110306415 A CN 201110306415A CN 103046113 A CN103046113 A CN 103046113A
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lead borate
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CN103046113B (en
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潘世烈
俞洪伟
吴红萍
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The present invention relates to a kind of boronic acid compound lead and boronic acid compound lead nonlinear optical crystal and preparation methods and purposes, the chemical formula of boronic acid compound lead and its nonlinear optical crystal is Pb4O (BO3) 2, crystal category rhombic system, space group Aba2, cell parameter are
Figure DSA00000588948800011
Figure DSA00000588948800012
Molecular weight 962.38, powder SHG effect reach 3 times of KDP (KH2PO4), transmission region 280nm to 3300nm. Boronic acid compound lead is synthesized using solid reaction process; Lead borate nonlinear optical crystal is grown using melt method or high temperature solution method, the lead borate nonlinear optical crystal mechanical hardness is moderate, easy to cut, polishing and preservation are used widely in the device for non-linear optical such as preparation times frequency generator, upper frequency converter, lower frequency converter or optical parametric oscillator.

Description

Compound lead borate and lead borate non-linear optic crystal and preparation method and purposes
Technical field
The present invention relates to chemical formula is Pb 4O (BO 3) 2Compound lead borate and lead borate non-linear optic crystal, crystal preparation method and the device for non-linear optical that utilizes this crystal to make.
Background technology
In laser technology, directly utilize the obtainable laser wavelength of laser crystals institute limited, from the ultraviolet to the infrared spectral region, remained sky white wave section.Use non-linear optic crystal, by non-linear optical effects such as frequency multiplication, mixing, optical parametric oscillations, limited optical maser wavelength can be converted to the laser of new wave band.Utilize this technology can fill up the blank spectral region of all kinds of Laser Devices Emission Lasers wavelength, laser apparatus is more widely used.
At present main non-linear optic crystal has: BBO (β-BBO), LBO (LiB 3O 5), CBO (CsB 3O 5), CLBO (CsLiB 6O 10) and KBBF (KBe 2BO 3F 2).Although the growing technology of these crystal reaches its maturity, but still exist obvious weak point:, layer growth habit long such as the easy deliquescence of crystal, growth cycle seriously and expensive etc.Therefore, seek new non-linear optical crystal material and remain an extremely important and large order.
Thereby in recent years, when the Development of Novel non-linear optic crystal, more and more pay attention to the preparation characteristic of crystal, wish that new crystalline material prepares excellent performance easily.The positively charged ion that introducing is easy to second order ginger Taylor distortion occurs in boron oxygen framework is with under the design philosophy guidance that improves its performance, and negatively charged ion is take boron oxygen functional motif as the basis, and its band gap is larger, and the two-photon absorption probability is little; Laser damage threshold is higher; Be beneficial to the stronger non-linear optical effect of acquisition; The B-O key is beneficial to the wide band light transmission.Cation selective contains the Pb of lone-pair electron 2+Ion, larger distortion occurs owing to jahn teller effect makes structure in it, thereby is conducive to produce large SHG effect.
Summary of the invention
The object of the invention is to provide a kind of compound lead borate and lead borate non-linear optic crystal, and chemical formula is Pb 4O (BO 3) 2
Another purpose of the present invention is to provide the preparation method who adopts solid reaction process synthetic compound and melting method or high temperature solution method growth lead borate non-linear optic crystal.
Further object of the present invention provides a kind of purposes of lead borate device for non-linear optical, for the preparation of frequency multiplication producer, upper or lower frequency transmodulator or optical parametric oscillator.
A kind of compound lead borate of the present invention, the chemical formula of this compound is Pb 4O (BO 3) 2, molecular weight 962.38 adopts the solid reaction process synthetic compound.
Described compound is 2: 1 leaded and boron-containing compound of mol ratio.
Lead-containing compounds is lead carbonate, lead nitrate, plumbous oxide, plumbic acetate or lead oxalate; Boron-containing compound is boric acid or boron oxide.
A kind of lead borate non-linear optic crystal, the chemical formula of this crystal are Pb 4O (BO 3) 2, do not have symmetry centre, belong to rhombic system, spacer Aba2, unit cell parameters is
Figure BSA00000588949100021
Figure BSA00000588949100022
Z=8,
The preparation method of described compound lead borate non-linear optic crystal adopts the solid reaction process synthetic compound, adopts the compound melt method for crystal growth again or adds the solubility promoter growing crystal, and concrete operations follow these steps to carry out:
A, the lead borate compound is heated to fusing in crucible, is heated to temperature 370-800 ℃, constant temperature 5-80 hour, obtain the blend melt of lead borate; Or will add fusing assistant in the lead borate compound, and be heated to temperature 370-800 ℃, constant temperature 5-80 hour, obtain the mixed molten liquid of boracic lead plumbate and fusing assistant, wherein the mol ratio of lead borate compound and fusing assistant is 1: 0.1-3;
B, preparation lead borate seed crystal: blend melt or mixed molten liquid that step a obtains slowly are down to room temperature with the speed of temperature 0.5-10 ℃/h, and spontaneous crystallization obtains the lead borate seed crystal;
C, will fill blend melt that step a makes or the crucible of mixed molten liquid is inserted in the crystal growing furnace, the seed crystal that step b is obtained is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 5-60 minute, seed crystal is carried out melt back in contact mixed molten liquid liquid level or mixed molten liquid body, constant temperature time 5-60 minute, be cooled to temperature 350-600 ℃ with the speed of temperature 1-60 ℃/h;
D, again with temperature 0.1-5 ℃/day speed slow cooling, carry out the growth of crystal with 0-60rpm rotating speed rotary seed crystal rod, after required yardstick is arrived in single crystal growing, crystal is lifted from the mixed molten liquid surface, and be down to room temperature with temperature 1-80 ℃/h speed, then crystal is taken out from burner hearth, can obtain the lead borate non-linear optic crystal.
The described fusing assistant of step a is PbO-H 3BO 3, H 3BO 3Or PbO, fusing assistant PbO-H 3BO 3In the system, PbO and H 3BO 3Mol ratio be 1-3: 1-4.
The described compound melt method for crystal growth of step b comprises crystal pulling method, kyropoulos or crucible Mobile Method.
Described lead borate non-linear optic crystal, the purposes in preparation frequency multiplication producer, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
Lead borate compound provided by the invention, chemical formula are Pb 4O (BO 3) 2, adopt solid reaction process to prepare the lead borate compound by following chemical equation:
(1)4PbCO 3+2H 3BO 3→Pb 4O(BO 3) 2+4CO 2↑+3H 2O↑
(2)4Pb(NO 3) 2+2H 3BO 3→Pb 4O(BO 3) 2+8NO 2↑+3H 2O↑+2O 2↑
(3)4PbO+2H 3BO 3→Pb 4O(BO 3) 2+9H 2O↑
(4)4PbC 2O 4+2H 3BO 3→Pb 4O(BO 3) 2+4CO 2↑+3H 2O↑+4CO↑
(5)4Pb(CH 3COO) 2+2H 3BO 3→Pb 4O(BO 3) 2+16CO↑+15H 2O↑
(6)4PbCO 3+B 2O 3→Pb 4O(BO 3) 2+4CO 2↑
(7)4Pb(NO 3) 2+B 2O 3→Pb 4O(BO 3) 2+8NO 2↑+2O 2↑
(8)4PbO+B 2O 3→Pb 4O(BO 3) 2
(9)4PbC 2O 4+B 2O 3→Pb 4O(BO 3) 2+4CO 2↑+4CO↑
(10)4Pb(CH 3COO) 2+B 2O 3→Pb 4O(BO 3) 2+4CO 2↑+12H 2O↑
The crystal that obtains has wider transmission region, and hardness is moderate, good mechanical property, and not easily broken and deliquescence is easy to the advantages such as processing and preservation.The device for non-linear optical that the compound lead borate non-linear optic crystal that adopts the method for the invention to obtain is made, at room temperature, make light source with the Nd:YAG Q-switched laser, incident wavelength is the infrared light of 1064nm, output wavelength is the green laser of 532nm, and laser intensity is equivalent to KDP (KH 2PO 4) 3 times.
Description of drawings
Fig. 1 is Pb of the present invention 4O (BO 3) 2The X-ray diffraction figure of powder.
Fig. 2 is Pb of the present invention 4O (BO 3) 2The fundamental diagram of the device for non-linear optical that crystal is made, wherein 1 is laser apparatus, and 2 for sending light beam, and 3 is Pb 4O (BO 3) 2Crystal, 4 is outgoing beam, 5 is filter plate.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples:
Embodiment 1:(adopts melting method)
Synthetic lead borate (Pb 4O (BO 3) 2) compound:
Adopt the synthetic lead borate compound of solid reaction process, its chemical equation is: 4Pb (NO 3) 2+ 2H 3BO 3→ Pb 4O (BO 3) 2+ 8NO 2↑+3H 2O ↑+2O 2↑;
With Pb (NO 3) 2, H 3BO 3Put into mortar at 2: 1 with stoichiometric ratio, mix and carefully grinding, in the opening corundum crucible of the Φ 400mm * 400mm that then packs into, with its compression, put into retort furnace, slowly be warming up to 300 ℃, constant temperature 24 hours, take out after cooling crucible, this moment, sample was more loose, then took out sample and again ground evenly, place again crucible, in retort furnace, in 430 ℃ of temperature constant temperature 48 hours again, with its taking-up, put into mortar and smash grinding to pieces and namely get the lead borate compound.This product is carried out X-ray analysis, gained X-ray spectrogram and Pb 4O (BO 3) 2The monocrystalline last X-ray spectrogram of pulverizing is consistent.
In melt, adopt Czochralski grown Pb 4O (BO 3) 2Crystal:
A, with synthetic Pb 4O (BO 3) 2Compound is packed in the opening platinum crucible of Φ 100mm * 100mm, is heated to 800 ℃ of temperature, and constant temperature obtained the blend melt of lead borate after 80 hours;
B, preparation lead borate seed crystal: the blend melt that step a obtains slowly is down to room temperature with the speed of 10 ℃/h of temperature, and spontaneous crystallization obtains the lead borate seed crystal;
C, the crucible that will fill the blend melt that step a makes are inserted in the crystal growing furnace, the seed crystal that step b is obtained is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 5 minutes, seed crystal is carried out melt back in contact mixed molten liquid liquid level, constant temperature time 5 minutes is being cooled to 505 ℃ of temperature with the speed of 10 ℃/h of temperature;
D, again with the speed slow cooling of 1 ℃/day of temperature, carry out the growth of crystal with 50rpm rotating speed rotary seed crystal rod, pull rate is 15mm/h, strengthen pull rate when finishing growth, make crystal break away from melt liquid level, speed with 80 ℃/h is down to room temperature, then takes out lentamente crystal from burner hearth, can obtain to be of a size of the Pb of 40mm * 34mm * 15mm 4O (BO 3) 2Crystal.
Press embodiment 1 described method, reaction formula 4Pb (NO 3) 2+ B 2O 3→ Pb 4O (BO 3) 2+ 8NO 2↑+2O 2↑ synthetic Pb 4O (BO 3) 2Compound also can obtain Pb 4O (BO 3) 2Crystal.
Embodiment 2:
Press reaction formula 4PbO+2H 3BO 3→ Pb 4O (BO 3) 2+ 9H 2O ↑ synthetic Pb 4O (BO 3) 2Compound, concrete operation step carries out according to embodiment 1;
Adopt crystal pulling method to prepare Pb 4O (BO 3) 2Crystal:
A, with synthetic Pb 4O (BO 3) 2Compound is put into the opening platinum crucible of Φ 90mm * 90mm, is heated to 370 ℃ of temperature, and constant temperature 5 hours obtains the blend melt of lead borate;
B, preparation lead borate seed crystal: blend melt or mixed molten liquid that step a obtains slowly are down to room temperature with the speed of 0.5 ℃/h of temperature, and spontaneous crystallization obtains the lead borate seed crystal;
C, the crucible that will fill the blend melt that step a makes are inserted in the crystal growing furnace, and the seed crystal that step b is obtained is along the Pb of c-axis cutting 4O (BO 3) 2Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof section aperture seed crystal is imported crucible, and first preheating seed crystal 5 minutes carries out melt back with seed crystal down to contact mixed molten liquid liquid level, and constant temperature time 5 minutes is being cooled to 350 ℃ of temperature with the speed of 1 ℃/h of temperature;
D, again with the speed slow cooling of 0.1 ℃/day of temperature, carry out the growth of crystal with 20rpm rotating speed rotary seed crystal rod, pull rate is 0.1mm/h, strengthen pull rate when finishing growth, make crystal break away from melt liquid level, speed with 40 ℃/h is down to room temperature, then takes out lentamente crystal from burner hearth, can obtain to be of a size of the Pb of 45mm * 35mm * 16mm 4O (BO 3) 2Crystal.
Press embodiment 2 described methods, reaction formula 4PbO+B 2O 3→ Pb 4O (BO 3) 2Synthetic Pb 4O (BO 3) 2Compound also can obtain Pb 4O (BO 3) 2Crystal.
Embodiment 3:(adopts melting method)
Press reaction formula 4PbC 2O 4+ 2H 3BO 3→ Pb 4O (BO 3) 2+ 4CO 2↑+3H 2O ↑+4CO ↑ synthetic Pb 4O (BO 3) 2Compound, concrete operation step carries out according to embodiment 1;
Adopt kyropoulos to prepare Pb 4O (BO 3) 2Crystal:
A, with synthetic Pb 4O (BO 3) 2The opening platinum crucible that compound is put into Φ 80mm * 80mm is heated to fusing, is heated to 450 ℃ of temperature, and constant temperature 25 hours obtains the blend melt of lead borate;
B, preparation lead borate seed crystal: the blend melt that step a obtains slowly is down to room temperature with the speed of 2 ℃/h of temperature, and spontaneous crystallization obtains the lead borate seed crystal;
C, the crucible that will fill the blend melt that step a makes are inserted in the crystal growing furnace, and the seed crystal that step b is obtained is along the Pb of c-axis cutting 4O (BO 3) 2Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof section aperture seed crystal is imported crucible, and first preheating seed crystal 15 minutes makes seed crystal contact with melt liquid level, carries out melt back, and constant temperature time 15 minutes is being cooled to 450 ℃ of temperature with the speed of 5 ℃/h of temperature;
D, again with the speed slow cooling of 2 ℃/day of temperature, carry out the growth of crystal with 30rpm rotating speed rotary seed crystal rod, after required yardstick is arrived in single crystal growing, crystal is lifted from the mixed molten liquid surface, and be down to room temperature with 20 ℃/h of temperature speed, then crystal is taken out from burner hearth, can obtain to be of a size of the Pb of Φ 40mm * 30mm * 12mm 4O (BO 3) 2Crystal.
Embodiment 4:(adopts melting method)
Press reaction formula 4Pb (CH 3COO) 2+ 2H 3BO 3→ Pb 4O (BO 3) 2+ 16CO ↑+15H 2O ↑ synthetic Pb 4O (BO 3) 2Compound, concrete operation step carries out according to embodiment 1;
Adopt kyropoulos to prepare Pb 4O (BO 3) 2Crystal
A, with synthetic Pb 4O (BO 3) 2The opening platinum crucible that compound is put into Φ 100mm * 100mm is heated to fusing, is heated to 500 ℃ of temperature, and constant temperature 45 hours obtains the blend melt of lead borate;
B, preparation lead borate seed crystal: blend melt or mixed molten liquid that step a obtains slowly are down to room temperature with the speed of 5 ℃/h of temperature, and spontaneous crystallization obtains the lead borate seed crystal;
C, the crucible that will fill the blend melt that step a makes are inserted in the crystal growing furnace, and the seed crystal that step b is obtained is along the Pb of c-axis cutting 4O (BO 3) 2Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof section aperture seed crystal is imported crucible, and first preheating seed crystal 25 minutes immerses in the melt seed crystal and carries out melt back, and constant temperature time 25 minutes is being cooled to 500 ℃ of temperature with the speed of temperature 45 C/h;
D, again with the speed slow cooling of 3 ℃/day of temperature, rotary seed crystal rod not, after required yardstick is arrived in single crystal growing, crystal is lifted from the mixed molten liquid surface, and be down to room temperature with 30 ℃/h of temperature speed, then crystal is taken out from burner hearth lentamente, can obtain to be of a size of the Pb of Φ 40mm * 35mm * 14mm 4O (BO 3) 2Crystal.
Press embodiment 4 described methods, reaction formula 4Pb (CH 3COO) 2+ B 2O 3→ Pb 4O (BO 3) 2+ 4CO 2↑+2H 2O ↑ synthetic Pb 4O (BO 3) 2Compound also can obtain Pb 4O (BO 3) 2Crystal.
Embodiment 5:(adopts o)
Press reaction formula 4Pb (NO 3) 2+ 2H 3BO 3→ Pb 4O (BO 3) 2+ 8NO 2↑+3H 2O ↑+2O 2↑ synthetic Pb 4O (BO 3) 2Compound, concrete operation step carries out according to embodiment 1;
Adopt o to prepare Pb 4O (BO 3) 2Crystal:
A, with synthetic Pb 4O (BO 3) 2Compound and fusing assistant H 3BO 3Pb in molar ratio 4O (BO 3) 2: H 3BO 3Be mixed at=1: 0.1, in the opening platinum crucible of the Φ 200mm * 200mm that packs into, is heated to fusing, is heated to 600 ℃ of temperature, and constant temperature 60 hours obtains the mixed molten liquid of boracic lead plumbate and fusing assistant;
B, preparation lead borate seed crystal: the mixed molten liquid that step a obtains slowly is down to room temperature with the speed of 7 ℃/h of temperature, and spontaneous crystallization obtains the lead borate seed crystal;
C, the crucible that will fill the mixed molten liquid that step a makes are inserted in the crystal growing furnace, and the seed crystal that step b is obtained is along the Pb of c-axis cutting 4O (BO 3) 2Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof section aperture seed crystal is imported crucible, and first preheating seed crystal 50 minutes carries out melt back under the immersed in liquid level, and constant temperature time 50 minutes is being cooled to 500 ℃ of temperature with the speed of 40 ℃/h of temperature;
D, again with the speed slow cooling of 0.5 ℃/day of temperature, carry out the growth of crystal with 60rpm rotating speed rotary seed crystal rod, after required yardstick is arrived in single crystal growing, crystal is lifted from the mixed molten liquid surface, and be down to room temperature with temperature 60 C/h speed, then crystal is taken out from burner hearth, can obtain to be of a size of the transparent Pb of 50mm * 30mm * 20mm 4O (BO 3) 2Crystal.
Press embodiment 5 described methods, reaction formula 4Pb (NO 3) 2+ B 2O 3→ Pb 4O (BO 3) 2+ 8NO 2↑+2O 2↑ synthetic Pb 4O (BO 3) 2Compound also can obtain Pb 4O (BO 3) 2Crystal.
Embodiment 6:(adopts o)
Press reaction formula 4PbO+2H 3BO 3→ Pb 4O (BO 3) 2+ 9H 2O ↑ synthetic Pb 4O (BO 3) 2Compound, concrete operation step carries out according to embodiment 1;
Adopt o to prepare Pb 4O (BO 3) 2Crystal:
A, with synthetic Pb 4O (BO 3) 2Compound and fusing assistant PbO be Pb in molar ratio 4O (BO 3) 2: PbO=1: 3 are mixed, and are heated to fusing in the opening platinum crucible of the Φ 100mm * 100mm that packs into, are heated to 800 ℃ of temperature, and constant temperature 80 hours obtains the mixed molten liquid of boracic lead plumbate and fusing assistant;
B, preparation lead borate seed crystal: step a mixed molten liquid slowly is down to room temperature with the speed of 10 ℃/h of temperature, and spontaneous crystallization obtains the lead borate seed crystal;
C, the crucible that will fill step a mixed molten liquid are inserted in the crystal growing furnace, and the seed crystal that step b is obtained is along the Pb of a axle cutting 4O (BO 3) 2Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof section aperture seed crystal is imported crucible, and first preheating seed crystal 60 minutes makes it to contact with liquid level and carries out melt back, and constant temperature time 60 minutes is being cooled to 600 ℃ of temperature with the speed of temperature 60 C/h;
D, again with the speed slow cooling of 0.1 ℃/day of temperature, rotary seed crystal rod not, after required yardstick is arrived in single crystal growing, crystal is lifted from the mixed molten liquid surface, and be down to room temperature with 10 ℃/h of temperature speed, then crystal is taken out from burner hearth, can obtain to be of a size of the transparent Pb of 50mm * 20mm * 10mm 4O (BO 3) 2Crystal.
Press embodiment 6 described methods, press reaction formula 4PbO+B 2O 3→ Pb 4O (BO 3) 2Synthetic Pb 4O (BO 3) 2Compound also can obtain Pb 4O (BO 3) 2Crystal.
Embodiment 7:(adopts o)
Press reaction formula 4PbC 2O 4+ 2H 3BO 3→ Pb 4O (BO 3) 2+ 4CO 2↑+3H 2O ↑+4CO ↑ synthetic Pb 4O (BO 3) 2Compound, concrete operation step carries out according to embodiment 1;
Adopt o to prepare Pb 4O (BO 3) 2Crystal:
A, with synthetic Pb 4O (BO 3) 2Compound and fusing assistant H 3BO 3-PbO was mixed in 1: 2 in molar ratio, wherein H 3BO 3With the PbO mol ratio be 3: 1, be heated to fusing in the opening platinum crucible of the Φ 150mm * 150mm that packs into, be heated to 650 ℃ of temperature, constant temperature 50 hours obtains the mixed molten liquid of boracic lead plumbate and fusing assistant;
B, preparation lead borate seed crystal: the mixed molten liquid that step a obtains slowly is down to room temperature with the speed of 10 ℃/h of temperature, and spontaneous crystallization obtains the lead borate seed crystal;
C, the crucible that will fill step a mixed molten liquid are inserted in the crystal growing furnace, and the seed crystal that step b is obtained is along the Pb of a axle cutting 4O (BO 3) 2Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof section aperture seed crystal is imported crucible, and first preheating seed crystal 35 minutes makes it to contact with liquid level and carries out melt back, and constant temperature time 35 minutes is being cooled to 550 ℃ of temperature with the speed of 15 ℃/h of temperature;
D, again with the speed slow cooling of 0.5 ℃/day of temperature, carry out the growth of crystal with 5rpm rotating speed rotary seed crystal rod, after required yardstick is arrived in single crystal growing, crystal is lifted from the mixed molten liquid surface, and be down to room temperature with 5 ℃/h of temperature speed, then crystal is taken out from burner hearth, can obtain to be of a size of the transparent Pb of 50mm * 30mm * 25mm 4O (BO 3) 2Crystal.
Press embodiment 7 described methods, press reaction formula 4PbC 2O 4+ B 2O 3→ Pb 4O (BO 3) 2+ 4CO 2↑+4CO ↑ synthetic Pb 4O (BO 3) 2Compound also can obtain Pb 4O (BO 3) 2Crystal.
Embodiment 8:
With embodiment 1-7 gained Pb arbitrarily 4O (BO 3) 2Crystal is by the frequency doubling device of the size 5mm * 5mm * 6mm of direction processing that is complementary, by being placed in shown in the accompanying drawing 2 on 3 the position, at room temperature, make light source with transferring Q Nd:YAG laser apparatus, incident wavelength is 1064nm, is that the infrared beam 2 of 1064nm is injected Pb by transferring QNd:YAG laser apparatus 1 to send wavelength 4O (BO 3) 2Monocrystalline 3, producing wavelength is the green frequency doubled light of 532nm, and output intensity is 3 times of equal conditions KDP, and it is the infrared light of 1064nm and the green glow of 532nm that outgoing beam 4 contains wavelength, obtains the green laser that wavelength is 532nm after filter plate 5 eliminations.

Claims (8)

1. compound lead borate, the chemical formula that it is characterized in that this compound is Pb 4O (BO 3) 2, molecular weight 962.38 adopts the solid reaction process synthetic compound.
2. compound as claimed in claim 1 is characterized in that this compound is 2: 1 leaded and boron-containing compound of mol ratio.
3. compound as claimed in claim 2 is characterized in that lead-containing compounds is lead carbonate, lead nitrate, plumbous oxide, plumbic acetate or lead oxalate; Boron-containing compound is boric acid or boron oxide.
4. lead borate non-linear optic crystal, the chemical formula that it is characterized in that this crystal is Pb 4O (BO 3) 2, do not have symmetry centre, belong to rhombic system, spacer Aba2, unit cell parameters is
Figure FSA00000588949000011
Figure FSA00000588949000012
Z=8,
Figure FSA00000588949000013
Figure FSA00000588949000014
5. the preparation method of compound lead borate non-linear optic crystal as claimed in claim 4, it is characterized in that adopting the solid reaction process synthetic compound, adopt the compound melt method for crystal growth again or add the solubility promoter growing crystal, concrete operations follow these steps to carry out:
A, the lead borate compound is heated to fusing in crucible, is heated to temperature 370-800 ℃, constant temperature 5-80 hour, obtain the blend melt of lead borate; Or will add fusing assistant in the lead borate compound, and be heated to temperature 370-800 ℃, constant temperature 5-80 hour, obtain the mixed molten liquid of boracic lead plumbate and fusing assistant, wherein the mol ratio of lead borate compound and fusing assistant is 1: 0.1-3;
B, preparation lead borate seed crystal: blend melt or mixed molten liquid that step a obtains slowly are down to room temperature with the speed of temperature 0.5-10 ℃/h, and spontaneous crystallization obtains the lead borate seed crystal;
C, will fill blend melt that step a makes or the crucible of mixed molten liquid is inserted in the crystal growing furnace, the seed crystal that step b is obtained is fixed on the seed rod, seed crystal under the crystal growing furnace top, elder generation's preheating seed crystal 5-60 minute, seed crystal is carried out melt back in contact mixed molten liquid liquid level or mixed molten liquid body, constant temperature time 5-60 minute, be cooled to temperature 350-600 ℃ with the speed of temperature 1-60 ℃/h;
D, again with temperature 0.1-5 ℃/day speed slow cooling, carry out the growth of crystal with 0-60rpm rotating speed rotary seed crystal rod, after required yardstick is arrived in single crystal growing, crystal is lifted from the mixed molten liquid surface, and be down to room temperature with temperature 1-80 ℃/h speed, then crystal is taken out from burner hearth, can obtain the lead borate non-linear optic crystal.
6. method as claimed in claim 5 is characterized in that the described fusing assistant of step a is PbO-H 3BO 3, H 3BO 3Or PbO, fusing assistant PbO-H 3BO 3In the system, PbO and H 3BO 3Mol ratio be 1-3: 1-4.
7. method as claimed in claim 6 is characterized in that the described compound melt method for crystal growth of step b comprises crystal pulling method, kyropoulos or crucible Mobile Method.
8. lead borate non-linear optic crystal as claimed in claim 4 is characterized in that, the purposes of this crystal in preparation frequency multiplication producer, upper frequency transmodulator, lower frequency transmodulator or optical parametric oscillator.
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CN104562196A (en) * 2013-10-23 2015-04-29 中国科学院新疆理化技术研究所 Compound lead borate hydrate nonlinear optical crystal and preparation method and use thereof
CN104746139A (en) * 2013-12-25 2015-07-01 中国科学院新疆理化技术研究所 Compound magnesium rubidium borate nonlinear optical crystal, preparation method and uses thereof
CN105019025A (en) * 2014-04-22 2015-11-04 中国科学院新疆理化技术研究所 Barium borosilicate bromine, barium borosilicate bromine nonlinear optical crystal, and preparation method and uses of barium borosilicate bromine nonlinear optical crystal
CN105568378A (en) * 2016-01-07 2016-05-11 西南科技大学 Preparation method of lead borate whisker with multiple functions and normal structure
CN105621361A (en) * 2014-11-08 2016-06-01 中国科学院新疆理化技术研究所 Compound lead chlorate, lead chlorate infrared nonlinear optical crystal, and preparation method and uses of lead chlorate infrared nonlinear optical crystal
CN106544731A (en) * 2015-09-19 2017-03-29 中国科学院新疆理化技术研究所 Lead chlorate infrared nonlinear optical crystal and preparation method and purposes
WO2020086014A1 (en) 2018-10-25 2020-04-30 Yeditepe Universitesi Use of mutant p53 gene targeted lead borate nanoparticles in cancer treatment and production method of these nanoparticles
CN114349017A (en) * 2022-01-14 2022-04-15 中国科学院新疆理化技术研究所 Compound strontium-zinc-boron-oxygen and strontium-zinc-boron-oxygen nonlinear optical crystal, and preparation method and application thereof
CN117305987A (en) * 2023-11-29 2023-12-29 北京青禾晶元半导体科技有限责任公司 Method for eliminating bubble wrapping in liquid phase method silicon carbide crystal growth process

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CN104213192A (en) * 2013-06-05 2014-12-17 中国科学院新疆理化技术研究所 Pb4B6O13 and Pb4B6O13 nonlinear optical crystal, preparation method and application thereof
CN104562196B (en) * 2013-10-23 2017-04-12 中国科学院新疆理化技术研究所 Compound lead borate hydrate nonlinear optical crystal and preparation method and use thereof
CN104562196A (en) * 2013-10-23 2015-04-29 中国科学院新疆理化技术研究所 Compound lead borate hydrate nonlinear optical crystal and preparation method and use thereof
CN104746139A (en) * 2013-12-25 2015-07-01 中国科学院新疆理化技术研究所 Compound magnesium rubidium borate nonlinear optical crystal, preparation method and uses thereof
CN105019025A (en) * 2014-04-22 2015-11-04 中国科学院新疆理化技术研究所 Barium borosilicate bromine, barium borosilicate bromine nonlinear optical crystal, and preparation method and uses of barium borosilicate bromine nonlinear optical crystal
CN105621361B (en) * 2014-11-08 2017-10-17 中国科学院新疆理化技术研究所 Compound lead chlorate and lead chlorate infrared nonlinear optical crystal and preparation method and purposes
CN105621361A (en) * 2014-11-08 2016-06-01 中国科学院新疆理化技术研究所 Compound lead chlorate, lead chlorate infrared nonlinear optical crystal, and preparation method and uses of lead chlorate infrared nonlinear optical crystal
CN106544731A (en) * 2015-09-19 2017-03-29 中国科学院新疆理化技术研究所 Lead chlorate infrared nonlinear optical crystal and preparation method and purposes
CN105568378A (en) * 2016-01-07 2016-05-11 西南科技大学 Preparation method of lead borate whisker with multiple functions and normal structure
WO2020086014A1 (en) 2018-10-25 2020-04-30 Yeditepe Universitesi Use of mutant p53 gene targeted lead borate nanoparticles in cancer treatment and production method of these nanoparticles
CN113164516A (en) * 2018-10-25 2021-07-23 耶迪特普大学 Application of lead borate nanoparticles targeting mutant p53 gene in cancer treatment and preparation method of nanoparticles
CN114349017A (en) * 2022-01-14 2022-04-15 中国科学院新疆理化技术研究所 Compound strontium-zinc-boron-oxygen and strontium-zinc-boron-oxygen nonlinear optical crystal, and preparation method and application thereof
CN117305987A (en) * 2023-11-29 2023-12-29 北京青禾晶元半导体科技有限责任公司 Method for eliminating bubble wrapping in liquid phase method silicon carbide crystal growth process
CN117305987B (en) * 2023-11-29 2024-03-12 北京青禾晶元半导体科技有限责任公司 Method for eliminating bubble wrapping in liquid phase method silicon carbide crystal growth process

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