CN1217037C - Non-linear optical crystal and use thereof - Google Patents
Non-linear optical crystal and use thereof Download PDFInfo
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- CN1217037C CN1217037C CN 02124079 CN02124079A CN1217037C CN 1217037 C CN1217037 C CN 1217037C CN 02124079 CN02124079 CN 02124079 CN 02124079 A CN02124079 A CN 02124079A CN 1217037 C CN1217037 C CN 1217037C
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Abstract
The present invention discloses a nonlinear optical crystal and an application thereof, which aims at providing a new nonlinear optical crystal compound, wherein the compound is easy to obtain a single crystal with large size. The nonlinear optical crystal compound provided by the present invention is cadmium zinc borate which has a molecular formula of (CdxZn<6-x>)B4O12, wherein X is an integer from 1 to 5, the space group of the compound is R3c, and unit cell parameter satisfies the following formulae: a=b=8.3867, c=12.2796, alpha=beta=90 degrees and gamma=120 degrees; the unit cell volume satisfies the following formulae: V=747.99 and Z=3; the crystal density satisfies the following formula: D=4.692 mg/m<3>. The cadmium zinc borate nonlinear optical crystal of the present invention can be widely applied to carry out laser wave length transformation, and can be used in laser wave length transformation devices, optical parameter devices, optical amplifiers, electro-optical modulators and optical waveguide devices.
Description
Technical Field
The invention relates to a nonlinear optical crystal and application thereof.
Background
With the development of laser technology, it is one of important issues to solve the problem of frequency conversion from visible light to ultraviolet and even deep ultraviolet region, and more specific issues include the development of all-solid-state vacuum ultraviolet laser light sources. Heretofore, a nonlinear optical crystal capable of directly generating a deep ultraviolet frequency-doubled wave output has been KBBF (KBe)2BO3F2) And SBBO (Sr)2Be2B2O7) However, both have a serious problem that it is difficult to obtain a single crystal because of its extreme difficulty in growing the single crystal.
From the crystal structure, KBBF (Chuangtian Chen, Zuyan Xu, Daoqun Deng, et al appl. Phys. Lett., 1996, 68 (21): 2930-3BeO of radicals and tetrahedrons4(or BeO)3F) Group composition, BO3The groups are arranged in parallel or approximately in parallel in the unit cell, keep the same direction, are the main structural sources of nonlinear optical effect, are connected with each other through tetrahedral structural groups to appropriately destroy the complete pi conjugated structure, and simultaneously lead BO3The three B-O dangling bonds of the group are replaced by oxygen bridges, thereby purple shifting the UV absorption edge of the crystal. However, because the two crystal structures are mainly characterized by an infinite two-dimensional network and the layers are connected by only weak electrostatic force or a small amount of bridging oxygen bonds, the layered growth habit is serious and large-size crystals are difficult to obtain.
Disclosure of Invention
The object of the present invention is to provide a novel nonlinear optical crystal compound which is relatively easy to obtain a large-sized single crystal.
The nonlinear optical crystal compound provided by the invention is cadmium zinc borate, and the molecular formula of the nonlinear optical crystal compound is (Cd)xZn6-x)B4O12Wherein X is an integer from 1 to 5, R3c is the space group of the compound, the unit cell parameters are a-b-8.3867 Å, c-12.2796 Å, α - β -90 degrees, gamma-120 degrees, and the unit cell volume V-747.99 Å3(ii) a And Z is 3. Crystal density D of 4.692g/cm3。
The non-linear optical crystal cadmium zinc borate can be widely applied to laser wavelength conversion, laser wavelength conversion devices, optical parameter and optical amplification devices, electro-optical modulation devices and optical waveguide devices.
The cadmium zinc borate can be synthesized by solid-phase reaction, and CdO, ZnO and H are weighed according to stoichiometric ratio3BO3After grinding and mixing evenly, the briquettes are put into a platinum crucible and sintered for 24 hours at a constant temperature of about 800 ℃ to obtain the pre-sintering material. The pre-sintering material is transferred to a platinum crucible with larger size, and cadmium zinc borate crystal with certain size can be obtained by adopting a pulling method or a flux method. The content of Cd and Zn in the obtained cadmium zinc borate crystal can be determined by adjusting the ratio of CdO to ZnO.
With (Cd)3Zn3)B4O12For example, it can be synthesized by the following solid phase reaction:
FIG. 1 is an X-ray powder diffraction pattern of the resulting single crystal. The cadmium zinc borate polycrystalline sample synthesized by the solid-phase reaction is confirmed to have strong powder frequency doubling effect through a powder frequency doubling test.
(Cd) was determined by plasma atomic emission spectrometry (ICP)3Zn3)B4O12The elemental composition of (a) was determined by single crystal structure measurement, and it was confirmed that the space group of the cadmium zinc borate crystal was R3c, the unit cell parameters were a ═ b ═ 8.3867 Å, c ═ 12.2796 Å ═ β ═ 90 °, γ ═ 120 °, and the unit cell volume V was V＝747.99Å3，Z＝3。
The structure of the cadmium zinc borate crystal is shown in figures 2-4, wherein 1 in figures 3 and 4 is BO3A planar triangular structure, 2 being MO4Tetrahedron (M ═ Cd, Zn). It can be seen from the figure that the crystal of the present invention has the following characteristics:
1. the crystal structure of the cadmium zinc borate is a plane triangle BO3Group and tetrahedral MO4(M ═ Cd, Zn) groups, all BO3The groups are all arranged in parallel on a planar layer perpendicular to the c-axis, and the close-packed plot along the c-axis shows BO per layer3The groups all have small-angle rotary dislocation, BO in each layer and between layers3All radicals passing through CdO4Tetrahedron and ZnO4The tetrahedra are connected to each other in such a way that they share a vertex oxygen atom. BO3The coplanar and equidirectional arrangement of the groups is very favorable for the superposition of the microscopic frequency doubling effect in the c-axis direction rather than the mutual offset, thereby having larger frequency doubling effect.
2. CdO due to disorder of Cd and Zn ions4Tetrahedron and ZnO4The tetrahedron can not be distinguished, and the proportion of the two tetrahedrons can be adjusted by changing the content of Cd and Zn in the raw material, so as to obtain (Cd)xZn6-x)B4O12(cadmium zinc borate) crystal.
3、CdO4And ZnO4The tetrahedron is obviously distorted, each Cd (Zn) -O bond length is different, the smallest O-Cd-O bond angle is 91.7 degrees, the largest is 127.9 degrees, and the difference is very large. Coupling BO3CdO of radicals4And ZnO4The tetrahedron plays an important role, on the one hand, because the tetrahedron generates obvious distortion, the tetrahedron is helpful to generate microscopic frequency doubling effect, and on the other hand, the tetrahedron firmly connects BO of different layers3The group makes it difficult to obtain a crystal of sufficient size for cadmium zinc borate crystal because of the layered growth habit like KBBF, SBBO, etc.
The cadmium zinc borate crystal has stable physical and chemical properties, no deliquescence in air and good mechanical properties.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a single crystal of the present invention.
FIG. 2 is a diagram of the crystal structure ORTEP of the present invention.
FIG. 3 is a close-packed view perpendicular to the c-axis of a crystal of the present invention, which is represented by a polyhedron.
FIG. 4 is a close-packed view along the c-axis of a crystal of the present invention shown as a polyhedron.
Detailed Description
Example 1 Synthesis of (Cd)3Zn3)B4O12
The used raw materials are as follows: CdO (20-40 mol%), ZnO (40-20 mol%), H3BO3(40 mol%). The mixture ratio of the raw materials is CdO, ZnO and H3BO330: 29: 41 (molar ratio).
CdO, ZnO and H are weighed according to the stoichiometric ratio3BO3After carefully grinding and uniformly mixing, the briquettes are put into a platinum crucible and sintered for 24 hours at a constant temperature of about 800 ℃ in a muffle furnace to obtain the pre-sintered material. Transferring the pre-sintering material to a platinum crucible with the diameter of 65X 50mm, placing the platinum crucible in a single crystal growth furnace, heating to about 950 ℃ to completely melt the pre-sintering material, and keeping the temperature constant for 48 hours under stirring to ensure that the melt is homogeneous. Stirring is carried out by rotating the crucible at 4.5 or 9rpm for a time t1After a stop time t2Then rotates in the reverse direction for a time t1(t1＝30～50t2) And repeating the steps. Cooling to a proper growth temperature (between 895 and 897 ℃), obtaining seed crystals by utilizing spontaneous crystallization, downwards extending the seed crystals to just contact the liquid surface, and cooling at a speed of 0.5-1 ℃/day to obtain transparent single crystals with the size of about 3 multiplied by 2 mm.
Claims (7)
1. A non-linear optical crystal compound of cadmium zinc borate with the molecular formula of (Cd)xZn6-x)B4O12Wherein X is an integer from 1 to 5, the space group of the compound is R3c, the unit cell parameters are a-b-8.3867 Å, c-12.2796 Å, α - β -90 degrees, gamma-120 degrees, the unit cell volume V-747.99 Å 3 and Z-3.
2. The nonlinear optical crystal cadmium zinc borate according to claim 1, wherein: the crystal density D of the compound is 4.692g/cm3。
3. Use of the nonlinear optical crystal in claim 1 to perform laser wavelength conversion.
4. Use of the nonlinear optical crystal in claim 1 in a laser wavelength conversion device.
5. Use of the nonlinear optical crystal in claim 1 in optical parametric and optical amplification devices.
6. Use of the nonlinear optical crystal of claim 1 in an electro-optic modulation device.
7. Use of the nonlinear optical crystal in claim 1 in an optical waveguide device.
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| CN 02124079 CN1217037C (en) | 2002-06-18 | 2002-06-18 | Non-linear optical crystal and use thereof |
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| CN101230071B (en) * | 2007-12-13 | 2010-12-08 | 上海交通大学 | Method for preparing non-linear optical metal-organic boron polymer crystal material |
| CN104532351B (en) * | 2014-12-05 | 2017-04-12 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal material, preparation method and application thereof |
| WO2016086426A1 (en) * | 2014-12-05 | 2016-06-09 | 中国科学院福建物质结构研究所 | Infrared nonlinear optical crystal material, method for preparation thereof, and application thereof |
| CN106757339A (en) * | 2016-11-29 | 2017-05-31 | 中国科学院福建物质结构研究所 | Halogen Firebrake ZB salt compound and its nonlinear optical crystal and growing method |
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