CN101514492B - Large size potassium strontium borate nonlinear optical crystal, preparation and use thereof - Google Patents

Large size potassium strontium borate nonlinear optical crystal, preparation and use thereof Download PDF

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CN101514492B
CN101514492B CN2009101132435A CN200910113243A CN101514492B CN 101514492 B CN101514492 B CN 101514492B CN 2009101132435 A CN2009101132435 A CN 2009101132435A CN 200910113243 A CN200910113243 A CN 200910113243A CN 101514492 B CN101514492 B CN 101514492B
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crystal
ksr
nonlinear optical
strontium borate
potassium strontium
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潘世烈
王永疆
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention relates to a large size potassium strontium borate nonlinear optical crystal, the preparation and use thereof. The formula of the crystal is: KSr4B3O9, which belongs to rhombic system, the space group is Pna2(1), and the molecular weight is 566.01, and the crystal size is 10-60mmx10-60mmx10-60mm. The preparation contains the following steps of: evenly mixing the potassium strontium borate compound with a fusing assistant, heating, maintaining the constant temperature, cooling to the saturation temperature and obtaining a mixture solution, placing a seed crystal into the mixture solution, lowering the temperature to the saturation temperature to obtain the required crystal, and subsequently extracting the crystal from the liquid level, cooling to room temperature, and finally obtaining the large size potassium strontium borate nonlinear optical crystal. The nonlinear optical effect of the crystal is approximately the same as the KDP, the transparent optical band is 220nm-3000nm. The crystal is simple in operation, low in cost, large in crystal size, short in growth period, less in coating, high in laster damage threshold, good in mechanical property, firm, stable in physicochemical properties, uneasy to deliquescence, convenient for processing and storage, or the like. Accordingly, the nonlinear optical crystal of the invention can be abroadly applied in nonlinearoptical devices such as frequency doubler, optical parametric oscillator or the like.

Description

Large size potassium strontium borate nonlinear optical crystal and its production and use
Technical field
The present invention relates to from the composite fluxing agent of optimizing, grow the large size nonlinear optical crystal potassium strontium borate, and potassium strontium borate crystal growth technique flow process and as the purposes of device for non-linear optical.
Background technology
Over past ten years, because based on deepening continuously of the communication and the social change of information, feasible non-linear optical crystal material (comprising laser frequency material, electrooptical material and photorefractive material) as one of important information material has obtained development fast, and has played more and more important effect in high-tech area.As utilize the crystalline frequency-doubled effect, and the frequency of laser is changed, widen the wavelength region of LASER Light Source, thereby obtained new LASER Light Source, laser apparatus is widely used.The all-solid state laser system has utilized the frequency doubling property of non-linear optic crystal to make, and it is little that it has a volume, light stability, and low cost and other advantages has wide application prospect.
Have been found that many non-linear optic crystals at present, and had some to obtain practical application, as: KDP, BBO, LBO, CLBO etc., they have the big and optic damage threshold value advantages of higher of nonlinear optical coefficients.But, because its saturating spectrographic ultraviolet is by the restriction of factors such as ABSORPTION EDGE or phase matched, do not obtain the various non-linear optic crystals that each wave band all is suitable for as yet, so the various countries scientist is still in exploration and the research of doing one's utmost paying close attention to all kinds of novel nonlinear optical crystals.
L.Wu etc. have at first reported potassium strontium borate KSr on Inorganic Chemistry magazine (Vol 45,3042-3047 (2006)) 4B 3O 9The existence of compound, and obtained KSr by polycrystal powder 4B 3O 9Structured data.a＝11.03843(8)
Figure G2009101132435D00011
b＝11.98974(9)
Figure G2009101132435D00012
c＝6.88446(5)
Figure G2009101132435D00013
V＝911.14(2)
Figure G2009101132435D00014
Z＝4。Need this crystalline size to reach the monocrystalline of several millimeters even centimetre-sized but test the basic physicals of a kind of crystalline (also comprising non-linear optical property), relevant as yet so far preparation size is enough to the KSr that uses for physical property measurement 4B 3O 9The report of monocrystalline more can't buy this crystal on market, the present invention is intended to prepare large size KSr 4B 3O 9Monocrystalline, and test its basic physicals.
Summary of the invention
The objective of the invention is in order to remedy the blank spectral region of all kinds of laser apparatus emission optical maser wavelengths, thus provide a kind of laser damage threshold more greatly, not deliquescence and have in ultraviolet, deep ultraviolet zone broad transparency range, have a transparent nonlinear optical crystal boric acid potassium strontium of centimetre-sized large size.
Another object of the present invention provides a kind of use fusing assistant, and is easy and simple to handle, the method for preparing the large size nonlinear optical crystal potassium strontium borate that growth cycle is short.
Another purpose of the present invention provides uses KSr 4B 3O 9The purposes of the device for non-linear optical that monocrystalline is made.
A kind of large size potassium strontium borate nonlinear optical crystal of the present invention, this crystal molecule formula is: KSr 4B 3O 9, belonging to rhombic system, molecular weight is 566.01, cell parameter is a=10.986 (2)
Figure G2009101132435D00021
B=11.929 (2)
Figure G2009101132435D00022
C=6.8831 (14)
Figure G2009101132435D00023
Spacer is Ama2.Its non-linear optical effect is equal to the non-linear optical effect with the KDP that tests under the condition approximately, and transmission region is from 220nm to 3000nm.Deliquescence not in air, growth cycle is short, and no inclusion is easy to processing and preservation, is suitable for making device for non-linear optical.
The preparation method of described large size potassium strontium borate nonlinear optical crystal adopts the flux method growing crystal, and concrete operations follow these steps to carry out:
A, potassium strontium borate polycrystal powder and the fusing assistant NaF and the H that will make with high temperature solid-state method 3BO 3Or KF and H 3BO 3In molar ratio 1: 1-4: the 1-4 mixing is put into crucible, is heated to 880-1100 ℃ with the temperature rise rate of 1-30 ℃/h, obtains containing KSr 4B 3O 9With the mixed molten liquid of fusing assistant, constant temperature 20-100 hour, be cooled fast to 836-865 ℃ again;
B, will be contained in the KSr that potassium strontium borate seed crystal on the seed rod is put into step a 4B 3O 9In the mixed molten liquid of fusing assistant, with 0-100 rev/min speed of rotation rotary seed crystal rod, slowly lower the temperature with 0.1-5 ℃/day speed more simultaneously;
C, treat that single crystal growing arrives near behind the crucible internal diameter yardstick, crystal is lifted from liquid level, reduce to room temperature, slowly from burner hearth, take out then, can obtain large size potassium strontium borate nonlinear optical crystal with 5-50 ℃/hour speed.
The described potassium strontium borate polycrystal powder of described step a is made by the mixture that contains potassium, contains strontium and boron-containing compound with equivalence ratio.
Potassic compound is preferably K 2O, KOH, KCl, K 2CO 3, KAc or KNO 3, the compound that contains strontium is preferably SrO, SrCl 2, SrCO 3Sr (Ac) 2Or Sr (NO 3) 2, the compound of boracic is preferably H 3BO 3Or B 2O 3
H in the described fusing assistant of step a 3BO 3Be preferably H 3BO 3Or B 2O 3
Seed crystal among the step b is that any direction is fixed on the seed rod.
The sense of rotation that seed crystal among the step b is fixed on the seed rod is unidirectional rotation or retrograde rotation.
Each folk prescription in the described reversible rotation is 1-10 minute to rotational time, and its timed interval is 0.1-1 minute.
Described large size nonlinear optical crystal potassium strontium borate can be used as preparation ultraviolet frequency double producer, go up or the purposes of lower frequency transmodulator or optical parametric oscillator.
Go up or lower frequency transmodulator, frequency multiplication producer or optical parametric oscillator comprise a branch of at least incidence electromagnetic radiation and produce the device that a branch of at least frequency is different from the output radiation of incidence electromagnetic radiation after by at least one block of non-linear optic crystal as preparation.
The present invention adopts general chemical synthesis process can prepare the potassium strontium borate polycrystal powder, polycrystal powder with preparation mixes (or adopting the potassium strontium borate starting raw material directly to mix in molar ratio) with fusing assistant again, can obtain large size potassium strontium borate nonlinear optical crystal.The present invention prepares the preferred solid reaction process of polycrystal powder, that is: after will containing K, Sr and B mol ratio and be 1: 4: 3 raw materials of compound and mixing, solid state reaction is carried out in heating, and can obtain chemical formula is KSr 4B 3O 9Compound.
Preparation KSr 4B 3O 9The chemical equation of polycrystalline compounds:
(1)K 2O+H 3BO 3+SrO→KSr 4B 3O 9+H 2O↑；
(2)K 2CO 3+B 2O 3+SrO→KSr 4B 3O 9+CO 2↑；
(3)KOH+H 3BO 3+Sr(NO 3) 2→KSr 4B 3O 9+H 2O↑+NO 2↑；
(4)KNO 3+H 3BO 3+Sr(NO 3) 2→KSr 4B 3O 9+NO 2↑；
(5)KNO 3+H 3BO 3+SrCO 3→KSr 4B 3O 9+CO 2↑+H 2O↑；
(6)K 2CO 3+H 3BO 3+SrCO 3→KSr 4B 3O 9+CO 2↑+H 2O↑；
(7)KCl+H 3BO 3+SrCl 2→KSr 4B 3O 9+Cl 2↑+H 2O↑；
(8)KAc+H 3BO 3+SrCO 3→KSr 4B 3O 9+CO 2↑+H 2O↑；
(9)K 2CO 3+H 3BO 3+Sr(Ac) 2→KSr 4B 3O 9+CO 2↑+H 2O↑；
Contain potassium among the present invention, contain strontium and boron-containing compound and fusing assistant and can adopt commercially available reagent and raw material.
According to the crystallography data of this large size potassium strontium borate nonlinear optical crystal, with crystal blank orientation; Press desired thickness and sectional dimension sliced crystal along the phase matched direction; With the logical light mirror polish of crystal, the potassium strontium borate crystal that processes promptly can be used as device for non-linear optical and uses.
Crystal provided by the present invention does not have particular requirement to the optics working accuracy.
Description of drawings.
Fig. 1 is KSr 4B 3O 9X-ray diffracting spectrum;
Fig. 2 is the fundamental diagram of the device for non-linear optical of large size potassium strontium borate crystal making of the present invention, and wherein (1) is laser apparatus, and (2) are convex lens, and (3) are large size potassium strontium borate nonlinear optical crystal, and (4) are beam splitting prism, and (5) are filter plate.
Embodiment
The present invention is described in detail below in conjunction with drawings and Examples:
Embodiment 1:
With reaction formula (1) is example: but be not limited to reaction formula (1)
K 2O+H 3BO 3+ SrO → KSr 4B 3O 9+ H 2O ↑ synthetic KSr 4B 3O 9Compound, the concrete operations step is as follows:
With K 2O, H 3BO 3, SrO puts into mortar with stoichiometric ratio, mix and careful the grinding, pack into then in the opening corundum crucible of Φ 200mm * 200mm, it is compressed, put into retort furnace, slowly be warming up to 450 ℃, constant temperature 5 hours, gas is driven out of as far as possible, take out crucible after cooling, sample is ground evenly, place crucible again, in retort furnace in 880 ℃ of constant temperature 5 hours again, take out after waiting its temperature to reduce to room temperature, the careful grinding is once more 880 ℃ of constant temperature 24 hours, put into mortar after the cooling, slight grinding just obtains sintering potassium strontium borate KSr completely 4B 3O 9Compound carries out X-ray analysis to this product again, and gained X-ray spectrogram and bibliographical information are in full accord;
Seed crystal is optimized: with synthetic KSr 4B 3O 9Compound and fusing assistant NaF and H 3BO 3, KSr in molar ratio 4B 3O 9: NaF: H 3BO 3=1: be mixed at 3: 1, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, be warming up to 1100 ℃, constant temperature is cooled to 860 ℃ after 30 hours, be cooled to 835 ℃ by 1 ℃/hour, and seed rod is put in the liquation, crystal accumulation is arranged on the seed rod surface, again by 2 ℃ of/day coolings, when waiting to accumulate in crystal diameter on the seed rod 30mm being arranged, reduce to room temperature by 30 ℃ of/hour speed, take out seed rod, choose the measured crystal of matter as seed crystal, put in the melt once more and grow, carry out seed crystal optimization;
With synthetic KSr 4B 3O 9Compound and fusing assistant NaF and H 3BO 3, KSr in molar ratio 4B 3O 9: NaF: H 3BO 3=1: be mixed at 3: 1, in the opening platinum crucible of the Φ 80mm * 80mm that packs into, be warming up to 1050 ℃, constant temperature is cooled to 836 ℃ after 30 hours, will be along the good KSr of optimization of a axle cutting 4B 3O 9Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, under the immersed in liquid level, seed crystal rotates with 100 rev/mins speed, constant temperature 0.5 hour, fast cooling to 845 ℃, lower the temperature with 2 ℃/day speed then, folk prescription is 5 minutes to rotational time, and its timed interval is 0.12 minute, treat that crystal growth finishes after, make crystal break away from liquid level, reduce to room temperature with 50 ℃ of/hour speed, slowly from burner hearth, take out then, can obtain to be of a size of the transparent KSr of 20mm * 10mm * 10mm 4B 3O 9Crystal.
K in the raw material 2O can be with corresponding KOH, KCl, K 2CO 3, KAc or KNO 3Replace; H 3BO 3The B of available respective amount 2O 3Replace, also can obtain KSr 4B 3O 9Monocrystalline.
Embodiment 2:
With reaction formula (2) is example: but be not limited to reaction formula (2)
K 2CO 3+ B 2O 3+ SrO → KSr 4B 3O 9+ CO 2↑ synthetic KSr 4B 3O 9Compound, the concrete operations step is carried out according to embodiment 1;
With synthetic KSr 4B 3O 9Compound and fusing assistant KF: H 3BO 3=1: be mixed at 1.5: 1.5, in the opening platinum crucible of the Φ 100mm * 100mm that packs into, be warming up to 1100 ℃, constant temperature is cooled to 865 ℃ after 100 hours, will optimize good KSr along (the seed crystal optimization among the embodiment 1) of the cutting of b axle 4B 3O 9Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, make it to contact with liquid level, seed crystal rotates with 50 rev/mins speed, folk prescription is 1 minute to rotational time, its timed interval is 0.1 minute, constant temperature 1 hour, fast cooling to 850 ℃, then with 5 ℃/day speed cooling, treat that crystal growth finishes after, make crystal break away from liquid level, reduce to room temperature with 30 ℃ of/hour speed, slowly from burner hearth, take out then, can obtain to be of a size of the transparent KSr of 60mm * 60mm * 20mm 4B 3O 9Crystal;
By the 2 described methods of enforcement, the K in the raw material 2CO 3Can use corresponding K 2O, KOH, KCl, KAc or KNO 3Replace.B 2O 3The H of available respective amount 3BO 3Replace, also can obtain KSr 4B 3O 9Monocrystalline.
Embodiment 3:
With reaction formula (4) is example: but be not limited to (4)
KNO 3+ H 3BO 3+ Sr (NO 3) 2→ KSr 4B 3O 9+ NO 2↑ synthetic KSr 4B 3O 9Compound, the concrete operations step is carried out according to embodiment 1;
With synthetic KSr 4B 3O 9Compound and fusing assistant NaF: H 3BO 3Be mixed in 1: 3: 2 in molar ratio, and in the opening platinum crucible of the Φ 110mm * 110mm that packs into, be warming up to 1000 ℃, constant temperature is cooled to 865 ℃ after 50 hours, will optimize good KSr along (the seed crystal optimization among the embodiment 1) of the cutting of a axle 4B 3O 9Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, make it to contact constant temperature 1 hour, fast cooling to 845 ℃ with liquid level, lower the temperature with 1 ℃/day speed then, after treating that crystal growth finishes, make crystal break away from liquid level, reduce to room temperature with 25 ℃ of/hour speed, slowly from burner hearth, take out then, can obtain to be of a size of the transparent KSr of 20mm * 20mm * 10mm 4B 3O 9Crystal.
By the 3 described methods of enforcement, the KNO in the raw material 3Can use corresponding K 2CO 3, K 2O, KOH, KAc, KCl replace H 3BO 3The B of available respective amount 2O 3Replace, also can obtain KSr 4B 3O 9Monocrystalline.
Embodiment 4:
With reaction formula (6) is example: but be not limited to (6)
K 2CO 3+ H 3BO 3+ SrCO 3→ KSr 4B 3O 9+ CO 2↑+H 2O ↑ synthetic KSr 4B 3O 9Compound, the concrete operations step is carried out according to embodiment 1;
With synthetic KSr 4B 3O 9Compound and fusing assistant KF: H 3BO 3Be mixed in 1: 3.5: 1 in molar ratio, and in the opening platinum crucible of the Φ 100mm * 100mm that packs into, be warming up to 950 ℃, constant temperature is cooled to 852 ℃ after 48 hours, will optimize good KSr along (the seed crystal optimization among the embodiment 1) of the cutting of a axle 4B 3O 9Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, make it to contact with liquid level, seed crystal rotates with 60 rev/mins speed, folk prescription is 6 minutes to rotational time, its timed interval is 0.8 minute, constant temperature 2 hours, fast cooling to 845 ℃, then with 1.5 ℃/day speed cooling, treat that crystal growth finishes after, make crystal break away from liquid level, reduce to room temperature with 12 ℃ of/hour speed, slowly from burner hearth, take out then, can obtain to be of a size of the transparent KSr of 20mm * 15mm * 15mm 4B 3O 9Crystal.
00 by the 4 described methods of enforcement, the K in the raw material 2CO 3Can use corresponding KNO 3, K 2O, KOH, KCl replace H 3BO 3The B of available respective amount 2O 3Replace, also can obtain KSr 4B 3O 9Monocrystalline.
Embodiment 5:
Adopt the potassium strontium borate starting raw material directly to mix in molar ratio;
Preparation KSr 4B 3O 9Mixture, with KOH, H 3BO 3, Sr (NO 3) 2With NaF 1: 4: 4 in molar ratio: 1 prepares simultaneously, behind the uniform mixing, in the opening platinum crucible of the Φ 100mm * 80mm that packs into, is warming up to 880 ℃, and constant temperature is cooled to 848 ℃ after 20 hours, will optimize good KSr along (the seed crystal optimization among the embodiment 1) of the cutting of b axle 4B 3O 9Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, make it to contact with liquid level, seed crystal rotates with 15 rev/mins speed, folk prescription is 4 minutes to rotational time, its timed interval is 0.1 minute, constant temperature 1 hour, fast cooling to 845 ℃, then with 0.5 ℃/day speed cooling, treat that crystal growth finishes after, make crystal break away from liquid level, reduce to room temperature with 40 ℃ of/hour speed, slowly from burner hearth, take out then, can obtain to be of a size of the transparent KSr of 20mm * 20mm * 15mm 4B 3O 9Crystal.
Press embodiment 5 described methods, the KOH in the raw material can use corresponding K 2O, KNO 3, KAc, K 2CO 3, KCl replaces H 3BO 3The B of available respective amount 2O 3Replace, also can obtain KSr 4B 3O 9Monocrystalline.
Embodiment 6:
Adopt the potassium strontium borate starting raw material directly to mix in molar ratio;
Preparation KSr 4B 3O 9Mixture, with K 2CO 3, H 3BO 3, Sr (NO 3) 2With KF 1: 2.5: 2 in molar ratio: 1 prepares simultaneously, behind the uniform mixing, in the opening platinum crucible of the Φ 100mm * 80mm that packs into, be warming up to 1060 ℃, constant temperature is cooled to 851 ℃ after 30 hours, will optimize good KSr along (the seed crystal optimization among the embodiment 1) of the cutting of a axle 4B 3O 9Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, makes it to contact with liquid level, seed crystal rotates with 25 rev/mins speed, and reversible rotational time is 10 minutes, and its timed interval is 1 minute, constant temperature 3 hours, fast cooling to 845 ℃, then with 1 ℃/day speed cooling, treat that crystal growth finishes after, make crystal break away from liquid level, reduce to room temperature with 8 ℃ of/hour speed, slowly from burner hearth, take out then, can obtain to be of a size of the transparent KSr of 25mm * 25mm * 10mm 4B 3O 9Crystal.
Press embodiment 6 described methods, the K in the raw material 2CO 3Can be with corresponding KOH, K 2O, KAc, KNO 3, KCl replaces, boric acid can be replaced with the boron oxide of respective amount, also can obtain KSr 4B 3O 9Monocrystalline.
Embodiment 7:
Adopt the potassium strontium borate starting raw material directly to mix in molar ratio;
Preparation KSr 4B 3O 9Mixture, with KNO 3, B 2O 3, Sr (NO 3) 2With NaF 1: 3: 1 in molar ratio: 1 prepares simultaneously, behind the uniform mixing, in the opening platinum crucible of the Φ 100mm * 80mm that packs into, be warming up to 1100 ℃, constant temperature is cooled to 853 ℃ after 20 hours, will optimize good KSr along (the seed crystal optimization among the embodiment 1) of the cutting of b axle 4B 3O 9Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, make it to contact with liquid level, seed crystal rotates with 80 rev/mins speed, folk prescription is 8 minutes to rotational time, its timed interval is 0.5 minute, constant temperature 2 hours, fast cooling to 845 ℃, then with 0.5 ℃/day speed cooling, treat that crystal growth finishes after, make crystal break away from liquid level, reduce to room temperature with 50 ℃ of/hour speed, slowly from burner hearth, take out then, can obtain to be of a size of the transparent KSr of 20mm * 20mm * 10mm 4B 3O 9Crystal;
Press embodiment 7 described methods, the KNO in the raw material 3Can use corresponding K 2CO 3, KOH, KAc, K 2O, KCl replace, B 2O 3The H of available respective amount 3BO 3Replace, also can obtain KSr 4B 3O 9Monocrystalline.
Embodiment 8:
Adopt the potassium strontium borate starting raw material directly to mix in molar ratio;
Preparation KSr 4B 3O 9Mixture, with K 2CO 3, H 3BO 3, SrCO 3With NaF 1: 2: 2 in molar ratio: 1 prepares simultaneously, behind the uniform mixing, in the opening platinum crucible of the Φ 100mm * 100mm that packs into, be warming up to 1080 ℃, constant temperature is cooled to 847 ℃ after 80 hours, will optimize good KSr along (the seed crystal optimization among the embodiment 1) of the cutting of a axle 4B 3O 9Seed crystal is fixed on the seed rod lower end with platinum filament, from furnace roof portion aperture seed crystal is imported crucible, make it to contact with liquid level, seed crystal rotates with 5 rev/mins speed, reversible rotational time is 2 minutes, its timed interval is 0.3 minute, constant temperature 1.5 hours, fast cooling to 845 ℃, then with 1.2 ℃/day speed cooling, treat that crystal growth finishes after, make crystal break away from liquid level, reduce to room temperature with 30 ℃ of/hour speed, slowly from burner hearth, take out then, can obtain to be of a size of the transparent KSr of 25mm * 25mm * 15mm 4B 3O 9Crystal;
Press embodiment 8 described methods, the K in the raw material 2CO 3Can be with corresponding KOH, K 2O, KAc, KNO 3, KCl replaces, boric acid can also can obtain KSr with the replacement of respective amount boron oxide 4B 3O 9Monocrystalline.
Embodiment 9:
KSr with embodiment 1-8 gained 4B 3O 9Crystal is by the frequency doubling device of the size 5mm * 5mm * 10mm 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 the 1064nm output of transferring Q Nd:YAG laser apparatus, observe tangible 532nm frequency multiplication green glow output, the frequency-doubled effect that output intensity is about equal conditions KDP is suitable;
Figure 4 shows that, be that the infrared beam of 1064nm is injected KSr through convex lens 2 by transferring Q Nd:YAG laser apparatus 1 to send wavelength 4B 3O 9Single crystal 3, producing wavelength is the green frequency doubled light of 532nm, it is the infrared light of 1064nm and the green glow of 532nm that outgoing beam 4 contains wavelength, obtains the frequency doubled light that wavelength is 532nm after filter plate 5 eliminations.
Embodiment 10:
KSr with embodiment 1-8 gained 4B 3O 9Crystal is pressed accompanying drawing 2 shown devices in 3 position by the optical parametric oscillation device of the size 5mm * 5mm * 10mm of direction processing that is complementary, at room temperature, uses the 532nm laser pumping, obtains the tuning output of parametric oscillation.

Claims (9)

1. centimetre-sized large size nonlinear optical crystal potassium strontium borate, this crystal molecule formula is: KSr 4B 3O 9, belonging to rhombic system, molecular weight is 566.01, cell parameter is
Figure FSB00000522150700012
Figure FSB00000522150700013
2. the preparation method of centimetre-sized large size nonlinear optical crystal potassium strontium borate according to claim 1 is characterized in that adopting the flux method growing crystal, and concrete operations follow these steps to carry out:
A, potassium strontium borate polycrystal powder and the fusing assistant NaF and the H that will make with high temperature solid-state method 3BO 3Or KF and H 3BO 3In molar ratio 1: 1-4: the 1-4 mixing is put into crucible, is heated to 880-1100 ℃ with the temperature rise rate of 1-30 ℃/h, obtains containing KSr 4B 3O 9With the mixed molten liquid of fusing assistant, constant temperature 20-100 hour, be cooled fast to temperature 836-865 ℃ again;
B, will be contained in the KSr that potassium strontium borate seed crystal on the seed rod is put into step a 4B 3O 9In the mixed molten liquid of fusing assistant, with 0-100 rev/min speed of rotation rotary seed crystal rod, slowly lower the temperature with 0.1-5 ℃/day speed more simultaneously;
C, treat that single crystal growing arrives near behind the crucible internal diameter yardstick, crystal is lifted from liquid level, reduce to room temperature, slowly from burner hearth, take out then, can obtain large size potassium strontium borate nonlinear optical crystal with 5-50 ℃/hour speed.
3. method according to claim 2 is characterized in that the described potassium strontium borate polycrystal powder of described step a made by the mixture that contains potassium, contains strontium and boron-containing compound with equivalence ratio.
4. method according to claim 3 is characterized in that potassic compound is preferably K 2O, KOH, KCl, K 2CO 3, KAc or KNO 3, the compound that contains strontium is preferably SrO, SrCl 2, SrCO 3Sr (Ac) 2Or Sr (NO 3) 2, the compound of boracic is preferably H 3BO 3Or B 2O 3
5. method according to claim 2 is characterized in that in the described fusing assistant of step a by H 3BO 3Replace with B 2O 3
6. method according to claim 2 is characterized in that the seed crystal among the step b is that any direction is fixed on the seed rod.
7. method according to claim 2 is characterized in that the sense of rotation that the seed crystal among the step b is fixed on the seed rod is unidirectional rotation or reversible rotation.
8. method according to claim 7 is characterized in that each folk prescription in the described reversible rotation is 1-10 minute to rotational time, and its timed interval is 0.1-1 minute.
9. centimetre-sized large size nonlinear optical crystal potassium strontium borate according to claim 1 preparation ultraviolet frequency double producer, on or application in lower frequency transmodulator or the optical parametric oscillator.
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CN103696006B (en) * 2012-09-28 2016-09-14 中国科学院新疆理化技术研究所 It is hydrated hydroxyl strontium borate and hydration hydroxyl strontium borate nonlinear optical crystal and preparation method and purposes
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CN109763169B (en) * 2019-03-06 2021-03-02 中国科学院新疆理化技术研究所 Potassium lutetium borate nonlinear optical crystal and its preparation method and use
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CN116443888B (en) * 2022-01-07 2024-04-12 中国科学院理化技术研究所 Potassium sodium strontium scandium borate compound, potassium sodium strontium scandium borate nonlinear optical crystal, preparation method and application thereof

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