CN1115431C - Sosoloid of magnesium zinc bromophosphate and its preparing process - Google Patents
Sosoloid of magnesium zinc bromophosphate and its preparing process Download PDFInfo
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- CN1115431C CN1115431C CN 01109761 CN01109761A CN1115431C CN 1115431 C CN1115431 C CN 1115431C CN 01109761 CN01109761 CN 01109761 CN 01109761 A CN01109761 A CN 01109761A CN 1115431 C CN1115431 C CN 1115431C
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Abstract
The present invention relates to an MgZnBPO sosoloid and a preparation method thereof, wherein 0<=x<=3. The preparation method comprises: after compounds containing Mg, Zn, P and B are uniformly mixed according to the molar ratio of the proportion of x: 3 to x: 1:1, the compounds are prepared by reaction and synthesis, wherein the compounds containing Mg and Zn are oxides, chloride, hydroxides, carbonates, nitrate, sulfate, and acetate or oxalate which contain Mg and Zn, the compound containing P is P2O5, and NH4H2PO4 or (NH4)2HPO4, and the compound containing B is B2O3 or H3BO3. The sosoloid can be made into nonlinear optical crystals, can be used for manufacturing frequency doubling generators, upper frequency converters or lower frequency converters, optical parametric oscillators, etc.
Description
The invention relates to a solid solution and a preparation method thereof, in particular to a magnesium zinc borophosphate solid solution and a preparation method thereof.
In modern laser technology, frequency conversion crystals are attracting attention because they effectively broaden the wavelength range of the laser. By utilizing the frequency doubling effect, the frequency mixing effect and the tunable optical parametric oscillation effect of the crystal, nonlinear optical devices such as a secondary harmonic generator, an upper frequency converter, a lower frequency converter, an optical parametric oscillator and the like can be manufactured. The laser generated by the laser can be subjected to frequency conversion through a nonlinear optical device, so that laser with more useful wavelengths can be obtained, and the method is an important means for obtaining a new laser light source. The full-curing blue-green laser system can be realized by generating near-infrared laser by a solid laser and then performing frequency conversion by a nonlinear optical crystal, and has huge application prospect in the technical field of laser.
The frequency doubling effect is the most important nonlinear optical effect. A beam of fundamental frequency light wave with frequency omega passes through a nonlinear optical crystal to generate a beam of frequency doubling light wave with frequency 2 omega, which is called frequency doubling effect. The crystal used for laser frequency doubling must be capable of realizing phase matching, and the frequency doubling conversion efficiency of the crystal can reach the maximum value when the phase matching condition is met. Phase matching can generally be achieved by an angular phase matching method, i.e.: a specific direction of the crystal is selected, the refractive indexes of the fundamental frequency light and the frequency doubling light in the direction are equal, and the phase matching condition can be met when the laser light propagates along the direction. For a uniaxial crystal, the phase match is related to the angle θ, which is the angle between the optical axis of the crystal and the direction of the incident light; for biaxial crystals, the phase matching is determined by θ, angle phi, which is the azimuthal angle of the incident light direction.
The main nonlinear optical material currently applied to blue-green light waveband frequency conversion is KTP (KTiOPO)4) Crystal (see Journal of Applied Physics, Vol.47, 4980, 1976, China science, B, Vol. (28), 235, 1985, BBO (β -BaB)2O4) Crystal and LBO disclosed in Chinese patent 88102084(LiB3O5) And (4) crystals. These materials have disadvantages in crystal growth: because KTP and LBO are melting compounds with different components, and BBO has phase change under the melting point, they need to use fluxing agent method to grow, the growth speed is slow, large-size crystal is not easy to obtain, the cost is high, and the large-scale application of the full-curing blue-green laser is influenced. Therefore, in recent years, when a novel nonlinear optical crystal is developed, not only optical properties and mechanical properties of the crystal but also production characteristics of the crystal are more and more important, and a new nonlinear optical crystal is desiredThe crystal material is easy to prepare, and preferably, a single crystal can be grown by a melt method, so that a large-size high-quality nonlinear optical crystal with low cost can be obtained. There are various melt growth techniques such as the Czochralski method, the crucible movement method, the top-seeded method, etc., and many theories have been made on the technical principles thereof.
The German journal Z.Kristallogr.160, 135-137, 1982 reports low-temperature phase zinc borophosphate α -Zn3BPO7And low temperature phase magnesium borophosphate α -Mg3BPO7Presence of α -Zn3BPO7Belongs to an orthorhombic system, the space group is Imm2, the unit cell parameters are a-8.438 (5) Å, b-4.884 (5) Å, c-12.746 (5) Å, and o-Mg3BPO7Also belongs to an orthorhombic system, the space group is Imm2, the unit cell parameters are a-8.497 (5) Å, b-4.880 (5) Å and c-12.558 (5) Å, and the two compounds have phase transition and have difficulty in crystal growth.
The invention aims to provide a chemical formula of MgxZn3-xBPO7X is more than 0 and less than 3;
another object of the present invention is to provide a compound represented by the formula MgxZn3-xBPO7X is more than 0 and less than 3.
The embodiments of the present invention are as follows:
the magnesium zinc borophosphate solid solution provided by the invention is characterized in that the chemical formula of the solid solution is MgxZn3-xBPO7Wherein x is more than 0 and less than 3;
the preparation method of the magnesium zinc borophosphate solid solution provided by the invention comprises the following steps: the raw materials of compounds containing Mg, Zn, P and B are uniformly mixed according to the molar ratio of x: 3-x: 1, and then solid phase reaction, hydrothermal reaction or coprecipitation reaction are carried out, thus obtaining the compound with the chemical expression of MgxZn3-xBPO7X is more than 0 and less than 3;
the Mg-containing compound is corresponding oxide, chloride, hydroxide, carbonate, nitrate, sulfate, acetate or oxalate containing Mg; the Zn-containing compound is corresponding oxide, chloride, hydroxide, carbonate, nitrate, sulfate, acetate or oxalate containing Zn; the compound containing P is P2O5、NH4H2PO4Or (NH)4)2HPO4(ii) a The compound containing B is B2O3Or H3BO3。
In principle, Mg can be prepared by general chemical synthesisxZn3-xBPO7X is more than 0 and less than 3, namely, uniformly mixing raw materials of compounds containing Mg, Zn, P and B according to the molar ratio of x: 3-x: 1, and then carrying out solid-phase reaction, hydrothermal reaction or coprecipitation reaction to obtain the solid solution with the chemical expression of MgxZn3-xBPO7And x is more than 0 and less than 3.
The following are typical of the available MgxZn3-xBPO70 < x < 3:
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
the magnesium zinc borophosphate solid solution provided by the invention can be prepared into magnesium zinc borophosphate nonlinear optical crystals with a chemical formula of MgxZn3-xBPO7Wherein 0 < x < 3; has no symmetry center, is a biaxial crystal, belongs to an orthorhombic system, has a space group of Imm2, is transparent in a wavelength range of 200-2500 nm, and has a Mohs hardness of 5.0.
The preparation method of the magnesium zinc borophosphate nonlinear optical crystal prepared from the magnesium zinc borophosphate solid solution provided by the invention comprises the following steps:
a. firstly, preparing a melt: mixing compounds containing Mg, Zn, B and P according to a molar ratio of x: 3-x: 1, grinding and uniformly mixing the raw materials, pre-sintering and sintering the raw materials, heating the raw materials in a crucible to be molten, and cooling the crucible to a temperature higher than the melting point of 1-5 ℃ to prepare a melt for later use;
b. rapidly growing crystals in the melt by using a melt method, wherein the melt method comprises a top seed crystal method, a pulling method and a crucible moving method;
the step of growing the crystal by the top seed crystal method comprises the following steps: fixing seed crystals on a seed crystal rod, contacting the seed crystals with the surface of the melt prepared in the crucible in the step a from the top, rotating the seed crystals and/or the crucible at the rotating speed of 0.1-80 rpm, and cooling at the speed of 0.1-5 ℃/day for growth; after the growth is finished, the crystal is separated from the liquid level of the melt, annealing is carried out at the speed of 1O-100 ℃/hour, then heating is stopped, and furnace cooling is carried out, thus obtaining the nonlinear optical crystal of the boron magnesium zinc phosphate solid melt;
the crystal growing method comprises the following steps: fixing a seed crystal on a seed crystal rod, contacting the seed crystal with the surface of the melt prepared in the crucible in the step a from the top, rotating the seed crystal and/or the crucible at the rotating speed of 0.1-80 rpm, and pulling the crystal upwards at the speed of 0.01-5 mm/h; after the growth is finished, enabling the crystal to be separated from the liquid level of the melt, annealing at the speed of 10-100 ℃/hour, then stopping heating, and cooling to room temperature along with the furnace to obtain the nonlinear optical crystal of the boron magnesium zinc phosphate solid melt;
the method for growing the crystal by the crucible moving method comprises the following steps: moving a crucible or a heater at the speed of 0.01-8 mm/h or slowly cooling a crystallization furnace to enable the melt to be solidified through a temperature gradient region to generate the nonlinear optical crystal of the boron-magnesium-zinc phosphate solid melt, wherein the heater is a resistance wire heater, a silicon-carbon rod heater or a silicon-molybdenum rod heater; the crucible is a cylindrical or boat-shaped crucible with a conical sharp corner at the bottom, and the movement is horizontal movement or vertical movement;
wherein, the compound raw material containing Mg is corresponding oxide, hydroxide, chloride, carbonate, nitrate, sulfate, acetate or oxalate containing Mg; the Zn-containing compound raw material is corresponding oxide, hydroxide, chloride, carbonate, nitrate, sulfate, acetate or oxalate containing Zn; the compound containing B is prepared from H3BO3Or B2O3(ii) a The compound raw material containing P is P2O5、NH4H2PO4Or (NH)4)2HPO4。
In principle, the existing melt growth technology can be used for preparing the magnesium zinc borophosphate crystal, and when a large-size crucible is adopted, the magnesium zinc borophosphate crystal with a corresponding larger size can be obtained.
The magnesium zinc borophosphate nonlinear optical crystal is used for manufacturing a nonlinear optical device, and the device comprises a device which generates at least one output radiation with different frequency from incident electromagnetic radiation after passing at least one incident electromagnetic radiation through at least one nonlinear optical crystal.
The boron magnesium zinc phosphate nonlinear optical crystal is transparent (as shown in figure 1), has an ultraviolet absorption edge of 200nm (as shown in figure 2), has a Mohs hardness of 5.0, is easy to cut, polish, process and store, is not deliquescent, and is suitable for manufacturing nonlinear optical devices.
The optical processing method of the crystal comprises the following steps: root of herbaceous plantAccording to the crystallographic data of the crystal, the crystal blank is oriented, the crystal is cut according to the required phase matching angles theta and phi, thickness and cross-section size, and the crystal light-passing surface is polished, thus the crystal can be used as a nonlinear optical device. The selection of the phase matching angles theta and phi depends on MgxZn3-xBPO7The value of x for the crystal. Details on the biaxial crystal phase matching angles θ and Φ are found in Journal of applied Physics, Vol.38, 4365, 1973, U.S.A. The optical processing method of the nonlinear optical crystal is familiar to the skilled person. The crystal provided by the invention has no special requirement on optical processing precision.
Compared with the prior non-linear optical crystal KTP, BBO and LBO preparation technology applied to blue-green light wave band frequency conversion, the boron-phosphorus acid magnesium zinc MgxZn3-xBPO7X is more than 0 and less than 3, the method is suitable for growing single crystals by using a melt method, the common melt growing method can be used, the melt viscosity of magnesium zinc borophosphate is lower than that of common borate, the mass transmission is facilitated, the crystals are easy to grow and are transparent and free of wrapping, the method has the advantages of no need of fluxing agent, simplicity in operation, high growth speed, low cost, easiness in obtaining larger-size crystals and the like, the growth cycle of the crystals such as BBO, LBO, KTP and the like is as long as 1 month to several months, and the growth cycle of the magnesium zinc borophosphate crystals only needs several days; compared with the common nonlinear optical crystals such as BBO, LBO, KTP and the like in the prior art, the magnesium zinc borophosphate crystal has better crystal preparation characteristics, and can grow a single crystal by using a melt method to obtain a large-size high-quality crystal with low price; the obtained crystal has the advantages of good mechanical property, difficult cracking, no deliquescence, easy processing and storage and the like; the nonlinear optical crystal of the invention is made into a nonlinear optical device with the cross section size of 5 multiplied by 5mm and the thickness of 7mm in the light transmission direction, and the thickness of the nonlinear optical device is adjusted by a Q-switched Nd: YAG laser with incident wavelength of 1064nm as light sourceInfrared light is emitted as green laser light having a wavelength of 532 nm.
The invention is further described below with reference to the following figures and examples:
FIG. 1 is a picture of a magnesium zinc borophosphate crystal;
FIG. 2 is a transmission spectrum of a magnesium zinc borophosphate crystal;
fig. 3 is a schematic diagram of a typical nonlinear optical device fabricated using magnesium zinc borophosphate crystals.
Wherein: laser 1 incident beam 2 boron magnesium zinc phosphate nonlinear optical crystal 3
Outgoing beam 4 filter 5
As can be seen from fig. 3, the laser 1 emits a light beam 2 to enter the magnesium zinc borophosphate nonlinear optical crystal 3, and the generated emergent light beam 4 passes through the filter 5, so as to obtain the required laser beam. The nonlinear optical device can be a frequency doubling generator, an upper frequency converter, a lower frequency converter, an optical parametric oscillator and the like. The laser 1 may be a neodymium-doped yttrium aluminum garnet (Nd: YAG) laser or other laser, for example, a laser using Nd: for a frequency doubling device using a YAG laser as a light source, an incident beam 2 is infrared light with the wavelength of 1064nm, green frequency doubling light with the wavelength of 532nm is generated through a boron magnesium zinc phosphate nonlinear optical crystal, an emergent beam 4 contains the infrared light with the wavelength of 1064nm and green light with the wavelength of 532nm, and a filter 5 is used for filtering infrared light components and only allowing the green frequency doubling light to pass through.
Example 1
Preparing the magnesium zinc borophosphate solid solution of the invention by high-temperature solid-phase reaction:
1. 2.033 g MgCl2·6H2O, 86.269 g Zn (NO)3)2·6H2O, 3.481 g of B2O3And 7.097 g P2O5Mixing uniformly (the mol ratio of Mg: Zn: B: P is 0.1: 2.9: 1), placing into a platinum crucible with a diameter of 40X 35mm, heating and melting in an electric furnace, keeping the temperature for 24 hours, cooling to room temperature at the speed of 150 ℃/h, grinding to obtain Mg0.1Zn2.9BPO7Solid solution polycrystalline like.
2. 12.036 g of MgSO425.078 g ZnCO36.183 g of H3BO3And 13.205 g (NH)4)2HPO4After being mixed evenly (the mol ratio is Mg: Zn: B)Adding into a platinum crucible with a diameter of 40 × 35mm, pre-sintering at 450 deg.C for 10 hr, sintering at 950 deg.C for 48 hr, and grinding to obtain Mg1Zn2BPO7A solid solution powder.
3. 38.46 g of Mg (NO)3)·6H2O, 14.909 g Zn (OH)26.183 g of H3BO3And 13.205 g (NH)4)2HPO4Mixing uniformly (the mol ratio of Mg: Zn: B: P is 1.5: 1), placing into a platinum crucible with phi of 40 × 35mm, placing the crucible into an electric furnace, presintering at 450 deg.C for 10 hr, keeping the temperature at 950 deg.C for 48 hr, sintering, and grinding to obtain Mg1.5Zn1.5BPO7A solid solution powder.
4. 20.279 g (MgCO)3)4·Mg(OH)2·5H2O, 11.323 g ZnO, 7.169 g H3BO3And 13.337 g NH4H2PO4Mixing uniformly (the mol ratio of Mg: Zn: B: P is 1.8: 1.2: 1), filling into phi 50Placing into a platinum crucible with opening of 35mm, placing the crucible into an electric furnace, pre-sintering at 450 deg.C for 10 hr, maintaining at 1000 deg.C for 48 hr, and grinding to obtain Mg1.8Zn1.2BPO7A solid solution powder.
5. 11.664 g of Mg (OH)213.629 g ZnCl26.183 g of H3BO3And 7.097 g P2O5Mixing uniformly (the mol ratio of Mg: Zn: B: P is 2: 1), placing into a platinum crucible with the diameter of 30X 30mm, heating and melting in an electric furnace, keeping the temperature for 24 hours, cooling to room temperature at the speed of 120 ℃/h, grinding to obtain Mg2Zn1BPO7A solid solution polycrystalline sample.
6. 20.15 g of MgO and 15.34 g of ZnC2O412.366 g of H3BO3And 14.194 g P2O5Mixing uniformly (the mol ratio of Mg: Zn: B: P is 2.5: 0.5: 1), placing into a platinum crucible with phi of 30 × 30mm, presintering at 500 deg.C for 15 hr, sintering at 1000 deg.C for 48 hr, and grinding to obtain Mg2.5Zn0.5BPO7A solid solution powder.
7. 32.574 g of MgC2O41.614 g ZnSO46.183 g of H3BO3And 7.097 g P2O5Mixing uniformly (the mol ratio of Mg: Zn: B: P is 2.9: 0.1: 1), placing into a platinum crucible with phi of 30 × 30mm, presintering at 500 deg.C for 10 hr, sintering at 1100 deg.C for 40 hr, and grinding to obtain Mg2.9Zn0.1BPO7A solid solution powder.
8. 51.469 g of Mg (C)2H3O2)2·4H2O, 79.024 g Zn (C)2H3O2)2·2H2O, 6.962 g of B2O3And 23.004 g of NH4H2PO4Mixing uniformly (the mol ratio of Mg: Zn: B: P is 1.2: 1.8: 1), placing into a platinum crucible with phi of 60 x 40mm, presintering at 500 deg.C for 10 hr, sintering at 1000 deg.C for 48 hr, and grinding to obtain magnesium-zinc borophosphate solid solution powder.
Example 2
The powdery magnesium zinc borophosphate solid solution of the invention is prepared by a hydrothermal method:
1. 2.015 g of MgO, 20.345 g of ZnO and 6.183 g of H3BO3And 11.502 g NH4H2PO4(the mol ratio is 0.5: 2.5: 1), then the mixture is put into an autoclave with the volume of phi 30mm multiplied by 140mm, 40ml of water is added, after sealing, the autoclave is put into a heating furnace, the temperature is raised to 250 ℃, and the constant temperature is kept for 48 hours; and closing the heating furnace, taking the high-pressure kettle out of the heating furnace when the furnace temperature is reduced to 50 ℃, naturally cooling to room temperature, and opening the high-pressure kettle to obtain the magnesium borophosphate zinc solid solution polycrystalline sample.
2. 27.621 g of Mg (NO)3)2·6H2O, 2.936 g ZnCl21.5 g of B2O3And 5.69 g (NH)4)2HPO4Mixing uniformly (the molar ratio of Mg: Zn: B: P is 2.5: 0.5: 1), loading into a high-pressure kettle with the volume of phi 30mm multiplied by 70mm, adding 30ml of water, sealing, placing the high-pressure kettle into a heating furnace, heating to 200 ℃, and keeping the temperature for 48 hours; the heating furnace is closed, and the temperature of the furnace is reduced to 80 DEG CAnd taking the high-pressure autoclave out of the heating furnace, naturally cooling to room temperature, and opening the high-pressure autoclave to obtain the magnesium-zinc borophosphate solid solution polycrystalline sample.Example 3
The coprecipitation method is used for preparing the powdery magnesium borophosphate zinc solid solution of the invention:
1. 9.758 g of MgCl2·6H2O, 39.267 g Zn (NO)3)2·6H2O, 3.71 g H3BO3And 7.923 g (NH)4)2HPO4(the mol ratio of Mg: Zn: B: P is 0.8: 2.2: 1) are respectively dissolved in 100mL of distilled water heated to 90 ℃, the solution is mixed and continuously stirred at 90 ℃, the solution is evaporated on an electric furnace to dryness, and the solution is sintered at 600 ℃ in a heating furnace to obtain Mg0.8Zn2.2BPO7Multiple crystal grains of (4).
2. 9.672 g of MgO and 5.963 g of Zn (OH)2Dissolving in nitric acid, adding water to prepare 200mL solution, and mixing 3.481 g of H3BO3And 11.502 g (NH)4)2HPO4Dissolving in 200mL distilled water heated to 90 deg.C, slowly mixing the above solutions, stirring, adjusting pH to 7 with 1: 1 ammonia water, and collecting the white precipitate as Mg2.4Zn0.6BPO7. After completion of the reaction, the pH was stabilized at 7, left to stand for 12 hours, and then the precipitate was separated from the solution by centrifugation, and the precipitate was washed with distilled water. And after drying, sintering the mixture in a heating furnace at 700 ℃ to obtain a powdery polycrystalline sample of the magnesium zinc borophosphate.
Example 4
Growing a boron-magnesium-zinc phosphate nonlinear optical crystal in a melt by adopting a pulling technology:
1. 51.515 g of Mg (OH)2391.86 g Zn (NO)3)2·6H2O, 45.248 g H3BO3And 96.641 g (NH)4)2HPO4Mixing uniformly (the mol ratio of Mg: Zn: B: P is 1.2: 1.8: 1), presintering at 450 deg.C for 10 hr, then sintering at 1000 deg.C for 24 hr, loading the obtained sample into phi 60mm × 40mm open platinum crucible, placing the crucible into crystal growth furnace, heating to meltAfter keeping the temperature for 10 hours, cooling to 5 ℃ higher than the crystallization temperature, fixing the seed crystal at the lower end of the seed crystal rod, and introducing the seed crystal into the crucible from a small hole at the top of the furnace to make the seed crystal contact with the liquid level of the melt to start crystal growth. The rotating speed of the seed rod is 20rpm, and the pulling speed is 0.5 mm/h; and finishing the growth to enable the crystal to be separated from the liquid level of the melt, annealing at the speed of 80 ℃/hour to reduce the temperature to 100 ℃, then stopping heating, and cooling the crystal to room temperature along with the furnace to obtain the magnesium zinc borophosphate nonlinear optical crystal with the size of 20mm multiplied by 15mm multiplied by 7 mm.
2. 14.882 g of MgCl2·6H2O, 342.705 g ZnSO425.481 g of B2O3And 51.95 grams of P2O5After uniform mixing (the mol ratio of Mg: Zn: B: P is 0.1: 2.9: 1), presintering at 400 ℃ for 10 hours, then sintering at 850 ℃ for 24 hours, putting the obtained sample into a platinum crucible with the opening diameter of 60mm multiplied by 40mm, putting the crucible into a crystal growth furnace, heating and melting, keeping the temperature for 5 hours, cooling to 4 ℃ higher than the crystallization temperature, then fixing the seed crystal at the lower end of a seed crystal rod, introducing the seed crystal into the crucible from a small hole at the top of the furnace, and enabling the seed crystal to contact with the liquid level of the melt to start crystal growth. The rotating speed of the seed rod is 40rpm, and the pulling speed is 0.4 mm/h; and when the growth is finished, enabling the crystal to be separated from the liquid level of the melt, annealing at the speed of 40 ℃/h, cooling to 100 ℃, and then stopping heating, so that the crystal is cooled to room temperature along with the furnace, thereby obtaining the boron magnesium zinc phosphate nonlinear optical crystal.Example 5
Preparing a boron-zinc magnesium phosphate nonlinear optical crystal by adopting a top seed crystal technology:
1. 52.170 g of MgSO4217.401 g ZnCO325.147 g of B2O3And 83.09 g NH4H2PO4Mixing uniformly (the mol ratio of Mg: Zn: B: P is 0.6: 2.4: 1), presintering at 450 deg.C for 10 hr, sintering at 900 deg.C for 24 hr, placing the obtained sample into phi 50mm × 40mm open platinum crucible, placing the crucible into crystal growth furnace, heating to melt, holding the temperature for 20 hr, cooling to 2 deg.C higher than crystallization temperature, fixing seed crystal at lower end of seed crystal rod by platinum wire, introducing seed crystal into crucible from small hole at furnace top, and making seed crystal be connected with melt surfaceAnd (3) cooling at the speed of 25rpm, namely, the seed rod rotates at the speed of 0.5 ℃/day, after the crystal growth is finished, lifting the crystal away from the liquid level of the melt, annealing at the speed of 100 ℃/hour, cooling to 100 ℃, stopping heating, and cooling to room temperature along with the furnace to obtain the magnesium zinc borophosphate nonlinear optical crystal with the thickness of 14mm multiplied by 10mm multiplied by 3.5 mm.
2. Mixing 56.42 g MgO, 69.573 g Zn (OH)243.281 g of H3BO3And 80.514 g NH4H2PO4Uniformly mixing (the molar ratio of Mg to Zn to B to P is 2: 1), presintering for 20 hours at 450 ℃, sintering for 30 hours at 1100 ℃, putting the obtained sample into a phi 60mm x 40mm open platinum crucible, putting the crucible into a crystal growth furnace, heating and melting, keeping the temperature for 2 hours, cooling to a temperature higher than the crystallization temperature by 1 ℃, fixing the seed crystal at the lower end of a seed crystal rod by a platinum wire, introducing the seed crystal into the crucible from a small hole at the top of the furnace, enabling the seed crystal to be in contact with the liquid level of a melt, rotating the seed crystal rod at a speed of 15rpm, cooling at a speed of 0.5 ℃/day, after the crystal growth is finished, lifting the crystal away from the liquid level of the melt, annealing at a speed of 100 ℃/hour, cooling to 100 ℃, stopping heating, and cooling to the room temperature along with the furnace to obtain the magnesium zinc boron phosphate nonlinear optical crystal.
Example 6
Preparing a boron-zinc magnesium phosphate nonlinear optical crystal by a crucible moving method:
1. mixing 1.363 g MgO, 3.361 g Zn (OH)20.785 g of B2O3And 1.6 g of P2O5Mixing uniformly (the mol ratio of Mg: Zn: B: P is 1.5: 1), placing into a platinum crucible with the diameter of phi 10mm, placing seed crystal at the bottom of the crucible, placing the crucible into a vertical heating furnace, heating until the raw materials are completely melted, keeping the heating power constant, and descending the crucible at the speed of 0.5 mm/h to solidify the melt from bottom to top to generate single crystal. After the crystallization is finished, annealing and cooling at the speed of 50 ℃/h to 100 ℃, stopping heating, and cooling to room temperature along with the furnace to obtain the magnesium zinc borophosphate nonlinear optical crystal with the size of phi 10mm multiplied by 30 mm.
2. 2.317 g of MgO, 0.936 g of ZnO and 0.801 g of B2O3And 1.632 g P2O5Mixing homogeneously (The mol ratio of Mg to Zn to B to P is 2.5 to 0.5 to 1), the mixture is put into a platinum crucible with the diameter of phi 12mm, the bottom of the crucible is provided with a conical sharp angle, seed crystals are placed at the bottom of the crucible, the crucible is put into a vertical heating furnace, the heating power is kept constant after the raw materials are heated to be completely melted, the crucible is descended at the speed of 0.1 mm/h to ensure that the melt is from the bottom to the bottomAnd (4) solidifying to generate a single crystal. And after the crystallization is finished, annealing and cooling at the speed of 30 ℃/hour to 100 ℃, stopping heating, and cooling to room temperature along with the furnace to obtain the boron magnesium zinc phosphate nonlinear optical crystal.
Example 7
Measuring the transmission spectrum of the magnesium zinc borophosphate nonlinear optical crystal obtained in the example 2-1 in the range of 200-2500 nm, wherein the crystal is transparent in the whole measuring range; the Mohs hardness of the material is 5.0, the material is not easy to crack, and the material is easy to cut, polish, process and store and is not deliquescent; the crystal is made into a frequency doubling device with the cross section size of 4.5 multiplied by 4.5mm and the thickness of 5mm in the light transmission direction, the frequency doubling device is arranged at the position of 3 according to the device shown in the attached drawing 3, and at room temperature, the frequency doubling device is formed by adjusting the Q Nd: YAG laser as light source with incident wavelength of 1064nm, and wavelength conversion by Q-switched Nd: YAG laser 1 emits infrared beam 2 with wavelength of 1064nm to enter MgxZn3-xBPO7The single crystal 3 generates green frequency doubling light with the wavelength of 532nm, the emergent light beam 4 contains infrared light with the wavelength of 1064nm and green light with the wavelength of 532nm, and the filter 5 filters the infrared light component to obtain green laser with the wavelength of 532 nm.
Those skilled in the art can easily manufacture other nonlinear optical devices, such as upper and lower frequency converters, etc., from the magnesium boro-phosphate zinc nonlinear optical crystal by using similar methods without departing from the spirit and scope of the present invention.
Claims (6)
1. A magnesium zinc borophosphate solid solution, which is characterized in that the chemical formula of the solid solution is MgxZn3-xBPO7Wherein x is more than 0 and less than 3.
2. A method for producing a magnesium zinc borophosphate solid solution according to claim 1, characterized in that: uniformly mixing the raw materials containing Mg, Zn, P and B compounds according to the molar ratio of x: 3-x: 1, and carrying out chemical synthesis reaction to generate the magnesium zinc borophosphate solid solution.
3. A method for producing a solid solution of magnesium zinc borophosphate according to claim 2, wherein said Mg-containing compound is a corresponding oxide, chloride, hydroxide, carbonate, nitrate, sulfate, acetate or oxalate containing Mg.
4. A method for producing a solid solution of magnesium zinc borophosphate according to claim 2, wherein said Zn-containing compound is a corresponding oxide, chloride, hydroxide, carbonate, nitrate, sulfate, acetate or oxalate containing Zn.
5. A process for the preparation of a solid solution of magnesium zinc borophosphate according to claim 2, wherein said P-containing compound is P2O5、NH4H2PO4Or (NH)4)2HPO4。
6. A process for the preparation of a solid solution of magnesium zinc borophosphate according to claim 2, wherein said B-containing compound is B2O3Or H3BO3。
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| CN 01109761 Expired - Fee Related CN1115431C (en) | 2001-04-10 | 2001-04-10 | Sosoloid of magnesium zinc bromophosphate and its preparing process |
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