ALKALI METAL MONOHYDROGEN CYANURATE COMPOUND, CRYSTAL THEREOF, PREPARATION METHOD THEREFOR AND USE THEREOF

Abstract

An alkali metal monohydrogen cyanurate compound of the chemical formula AM(HC.sub.3N.sub.3O.sub.3).nH.sub.2O (specifically such as KLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O, RbLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O, RbNa(HC.sub.3N.sub.3O.sub.3).2H.sub.2O) and a nonlinear optical crystal thereof are related to optoelectronic functional materials. Measured using a powder frequency doubling test method, and the powder frequency doubling effect of the nonlinear optical crystal is about 2-3 times that of KH.sub.2PO.sub.4 (KDP). The ultraviolet absorption edge of the nonlinear optical crystal is shorter than 250 nm. The nonlinear optical crystal can achieve the harmonic generator of double, triple, or quadruple frequency for Nd:YAG (λ=1.064 μm). Moreover, the nonlinear optical crystal is of a single crystalline structure, is colorless and transparent, and does not deliquesce in air.

Claims

1. An alkali metal monohydrogen cyanurate compound, characterized in that the chemical formula of the compound is AM(HC.sub.3N.sub.3O.sub.3).nH.sub.2O, wherein A and M are, the same or different, independently selected from alkali metals, for example Li, Na, K, Rb, Cs, Fr; n is selected from an integer of 0 or more.

2. The compound as claimed in claim 1, characterized in that n is an integer selected from 0-10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, specifically such as 2.

3. The compound as claimed in claim 1, characterized in that the compound is selected from potassium lithium monohydrogen cyanurate dihydrate (chemical formula: KLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O), rubidium lithium monohydrogen cyanurate dihydrate (chemical formula: RbLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O), rubidium sodium monohydrogen cyanurate dihydrate (chemical formula: RbNa(HC.sub.3N.sub.3O.sub.3).2H.sub.2O); preferably, the compound is in the form of a nonlinear optical crystal.

4. The compound as claimed in claim 1, characterized in that the compound is a nonlinear optical crystal of potassium lithium monohydrogen cyanurate dihydrate, the chemical formula of which is KLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O; preferably, the nonlinear optical crystal of potassium lithium monohydrogen cyanurate dihydrate has an X-ray powder diffraction pattern substantially as shown in FIG. 3; preferably, the nonlinear optical crystal of potassium lithium monohydrogen cyanurate dihydrate does not have a symmetry center, and belongs to an orthorhombic crystal system, with the space group Pna2(1), the cell parameters a=15.387(6) Å, b=3.6524(16) Å, c=12.755(6) Å, α=β=γ=90°, Z=4, and the unit cell volume V=716.82 Å.sup.3.

5. The compound as claimed in claim 1, characterized in that the compound is a nonlinear optical crystal of rubidium lithium monohydrogen cyanurate dihydrate, the chemical formula of which is RbLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O; preferably, the nonlinear optical crystal of rubidium lithium monohydrogen cyanurate dihydrate has an X-ray powder diffraction pattern substantially as shown in FIG. 4; preferably, the nonlinear optical crystal of rubidium lithium monohydrogen cyanurate dihydrate does not have a symmetry center, and belongs to an orthorhombic crystal system, with the space group Pna2(1), the cell parameters a=15.682(7) Å, b=3.7453(17) Å, c=12.768(6) Å, α=β=γ=90°, Z=4, and the unit cell volume V=749.9 Å.sup.3.

6. The compound as claimed in claim 1, characterized in that the compound is a nonlinear optical crystal of rubidium sodium monohydrogen cyanurate dihydrate, the chemical formula of which is RbNa(HC.sub.3N.sub.3O.sub.3).2H.sub.2O; preferably, the nonlinear optical crystal of rubidium sodium monohydrogen cyanurate dihydrate has an X-ray powder diffraction pattern substantially as shown in FIG. 5; preferably, the nonlinear optical crystal of rubidium sodium monohydrogen cyanurate dihydrate does not have a symmetry center, and belongs to an orthorhombic crystal system, with the space group Pna2(1), the cell parameters a=15.829(18) Å, b=3.964(5) Å, c=13.068(16) Å, α=β=γ=90°, Z=4, and the unit cell volume V=819.8 Å.sup.3.

7. A method for preparing the compound as claimed in claim 1, characterized in that the method for preparing includes reacting AOH.xH.sub.2O, MOH.yH.sub.2O with H.sub.3C.sub.3N.sub.3O.sub.3 to obtain the alkali metal monohydrogen cyanurate compound; wherein A and M have the definition given in claim 1; x and y are, the same or different, independently selected from an integer of 0 or more.

8. The method as claimed in claim 7, characterized in that x and y are, the same or different, independently an integer selected from 0-10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, preferably 0, 1; preferably, the molar ratio of the AOH.xH.sub.2O, MOH.yH.sub.2O and H.sub.3C.sub.3N.sub.3O.sub.3 is (0.5-2.5):(0.5-2.5):1, preferably (0.8-1.2):(0.8-1.2):1, such as 1:1:1; preferably, the reaction is carried out in a solvent, and the solvent is selected from an organic solvent or an inorganic solvent, preferably an inorganic solvent, such as water; preferably, the temperature of the reaction is 50-110° C., preferably 60-100° C., such as 80° C.

9. The method as claimed in claim 7, characterized in that, after the reaction is ended, the reaction liquid is cooled at a constant cooling rate; after cooling, the alkali metal monohydrogen cyanurate compound is obtained by washing with the solvent; preferably, the cooling rate is 1-10° C./hour, preferably 1-5° C./hour, such as 1° C./hour, 5° C./hour; preferably, the reaction liquid is cooled to 0-40° C., preferably 10-40° C., such as 10° C., 40° C.; preferably, the solvent used for the washing is water, acetone or a mixture thereof, such as acetone.

10. Use of the compound as claimed in claim 1, characterized in that the compound can be used for frequency conversion of laser output, harmonic generator in ultraviolet region, optical parametric amplifier and optical waveguide device; preferably, the compound achieves a harmonic light output of double, triple, quadruple, quintuple or sextuple frequency for a laser beam with a wavelength of 1.064 μm; preferably, the compound can be used for optical parametric amplifiers from infrared to ultraviolet region.

Description

DESCRIPTION OF FIGURES

[0036] FIG. 1 is a typical schematic diagram of nonlinear optical effects when KLHCY, RLHCY, RNHCY crystals are used as frequency doubling crystals, where 1 is a laser, 2 is an incident laser beam, 3 is a single crystal after crystal post-processing and optical processing, 4 is an output laser beam, 5 is a filter.

[0037] FIG. 2 is a schematic diagram of the structures of KLHCY, RLHCY, RNHCY crystals (KLHCY, RLHCY, RNHCY are isomorphic compounds).

[0038] FIG. 3 is the X-ray diffraction pattern of KLHCY single crystal after grinding into powder.

[0039] FIG. 4 is the X-ray diffraction pattern of RLHCY single crystal after grinding into powder.

[0040] FIG. 5 is the X-ray diffraction pattern of RNHCY single crystal after grinding into powder.

SPECIFIC MODE FOR CARRYING OUT THE INVENTION

[0041] As mentioned above, the present invention provides a compound with a new structure and its crystal, the structural formula of which is AM(HC.sub.3N.sub.3O.sub.3).nH.sub.2O (specifically such as KLHCY, RLHCY, RNHCY), in which monohydrogen cyanurate radical provides excellent aqueous solution growth performance and nonlinear performance for crystal growth.

[0042] The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

[0043] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products, or can be prepared by known methods.

Example 1

Preparation of KLi(HC.SUB.3.N.SUB.3.O.SUB.3.).2H.SUB.2.O, RbLi(HC.SUB.3.N.SUB.3.O.SUB.3.).2H.SUB.2.O and RbNa(HC.SUB.3.N.SUB.3.O.SUB.3.).2H.SUB.2.O Single Crystals by Aqueous Solution Method

[0044] Raw materials used for the preparation of KLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal:

TABLE-US-00001 KOH 3.44 g (0.06 mol) LiOH•H.sub.2O 2.60 g (0.06 mol) H.sub.3C.sub.3N.sub.3O.sub.3 7.74 g (0.06 mol) H.sub.2O 50 ml

[0045] The specific operation steps were as follows: the above raw materials weighed according to the above amounts were put into a 100 ml beaker, to which was put a magnetic bar; the beaker was placed on a magnetic heating stirrer; the beaker was heated to 80° C. with stirring, and then cooled to 40° C. at a cooling rate of 5° C./hour. After cooling, the sample was washed with acetone to obtain KLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal with a size of 5×1×1 mm.

[0046] Raw materials used for the preparation of RbLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal:

TABLE-US-00002 RbOH•H.sub.2O 7.23 g (0.06 mol) LiOH•H.sub.2O 2.60 g (0.06 mol) H.sub.3C.sub.3N.sub.3O.sub.3 7.74 g (0.06 mol) H.sub.2O 50 ml

[0047] The specific operation steps were as follows: the above raw materials weighed according to the above amounts were put into a 100 ml beaker, to which was put a magnetic bar; the beaker was placed on a magnetic heating stirrer; the beaker was heated to 80° C. with stirring, and then cooled to 40° C. at a cooling rate of 5° C./hour. After cooling, the sample was washed with acetone to obtain RbLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal with a size of 1×1×5 mm.

[0048] Raw materials used for the preparation of RbNa(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal:

TABLE-US-00003 NaOH 2.40 g (0.06 mol) RbOH•H.sub.2O 7.23 g (0.06 mol) H.sub.3C.sub.3N.sub.3O.sub.3 7.74 g (0.06 mol) H.sub.2O 50 ml

[0049] The specific operation steps were as follows: the above raw materials weighed according to the above amounts were put into a 100 ml beaker, to which was put a magnetic bar; the beaker was placed on a magnetic heating stirrer; the beaker was heated to 80° C. with stirring, and then cooled to 10° C. at a cooling rate of 5° C./hour. After cooling, the sample was washed with acetone to obtain RbNa(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal with a size of 1×5×1 mm.

Example 2

Preparation of KLi(HC.SUB.3.N.SUB.3.O.SUB.3.).2H.SUB.2.O, RbLi(HC.SUB.3.N.SUB.3.O.SUB.3.).2H.SUB.2.O and RbNa(HC.SUB.3.N.SUB.3.O.SUB.3.).2H.SUB.2.O Single Crystals by Aqueous Solution Method

[0050] Raw materials used for the preparation of KLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal:

TABLE-US-00004 KOH 3.44 g (0.06 mol) LiOH•H.sub.2O 2.60 g (0.06 mol) H.sub.3C.sub.3N.sub.3O.sub.3 7.74 g (0.06 mol) H.sub.2O 50 ml

[0051] The specific operation steps were as follows: the above raw materials weighed according to the above amounts were put into a 100 ml beaker, to which was put a magnetic bar; the beaker was placed on a magnetic heating stirrer; the beaker was heated to 80° C. with stirring, and then cooled to 40° C. at a cooling rate of 1° C./hour. After cooling, the sample was washed with acetone to obtain KLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal with a size of 5×2×2 mm.

[0052] Raw materials used for the preparation of RbLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal:

TABLE-US-00005 RbOH•H.sub.2O 7.23 g (0.06 mol) LiOH•H.sub.2O 2.60 g (0.06 mol) H.sub.3C.sub.3N.sub.3O.sub.3 7.74 g (0.06 mol) H.sub.2O 50 ml

[0053] The specific operation steps were as follows: the above raw materials weighed according to the above amounts were put into a 100 ml beaker, to which was put a magnetic bar; the beaker was placed on a magnetic heating stirrer; the beaker was heated to 80° C. with stirring, and then cooled to 40° C. at a cooling rate of 1° C./hour. After cooling, the sample was washed with acetone to obtain RbLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal with a size of 2×2×5 mm.

[0054] Raw materials used for the preparation of RbNa(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal:

TABLE-US-00006 NaOH 2.40 g (0.06 mol) RbOH•H.sub.2O 7.23 g (0.06 mol) H.sub.3C.sub.3N.sub.3O.sub.3 7.74 g (0.06 mol) H.sub.2O 50 ml

[0055] The specific operation steps were as follows: the above raw materials weighed according to the above amounts were put into a 100 ml beaker, to which was put a magnetic bar; the beaker was placed on a magnetic heating stirrer; the beaker was heated to 80° C. with stirring, and then cooled to 10° C. at a cooling rate of 1° C./hour. After cooling, the sample was washed with acetone to obtain RbNa(HC.sub.3N.sub.3O.sub.3).2H.sub.2O single crystal with a size of 2×5×2 mm.

Example 3

[0056] The KLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O, RbLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O and RbNa(HC.sub.3N.sub.3O.sub.3).2H.sub.2O crystals obtained in Example 2 were processed, cut, oriented and polished, and then placed at the position 3 in the device shown in FIG. 1. At room temperature, using Q-switch Nd:YAG laser as input light source, with incident wavelength of 1064 nm, an obvious 532 nm frequency doubling green light output was observed, with output intensity about 2-3 times that of KDP under the equal conditions. Specifically, the output intensity of KLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O crystal was about 3 times that of KDP under the equal conditions, the output intensity of RbLi(HC.sub.3N.sub.3O.sub.3).2H.sub.2O crystal was about 2 times that of KDP under the equal conditions, and the output intensity of RbNa(HC.sub.3N.sub.3O.sub.3).2H.sub.2O crystal was about 2 times that of KDP under the equal conditions.

[0057] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement and the like made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.