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).Math.nH.sub.2O (specifically such as KLi(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O, RbLi(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O, RbNa(HC.sub.3N.sub.3O.sub.3).Math.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 (=1.064 m). 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 having a formula of AM(HC.sub.3N.sub.3O.sub.3).Math.nH.sub.2O, wherein A and M are different and are independently selected from Li, Na, K, Rb, Cs, and Fr, and n is an integer of 0-10.

2. The compound of claim 1, wherein n is 2.

3. The compound of claim 1, selected from potassium lithium monohydrogen cyanurate dihydrate (KLi(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O), rubidium lithium monohydrogen cyanurate dihydrate (RbLi(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O), and rubidium sodium monohydrogen cyanurate dihydrate (RbNa(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O).

4. The compound of claim 1, wherein 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).Math.2H.sub.2O.

5. The compound of claim 1, wherein 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).Math.2H.sub.2O.

6. The compound of claim 1, wherein 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).Math.2H.sub.2O.

7. A method for preparing the compound of claim 1, comprising reacting AOH.Math.xH.sub.2O, MOH.Math.yH.sub.2O with H.sub.3C.sub.3N.sub.3O.sub.3 in a reaction liquid to obtain the alkali metal monohydrogen cyanurate compound, wherein x and y are, the same or different, independently 0 or more.

8. The method of claim 7, wherein a molar ratio of the AOH.Math.xH.sub.2O, MOH.Math.yH.sub.2O and H.sub.3C.sub.3N.sub.3O.sub.3 is (0.5-2.5):(0.5-2.5):1.

9. The method of claim 7, further comprising cooling the reaction liquid; and washing the obtained alkali metal monohydrogen cyanurate compound.

10. A method for frequency conversion of laser output, comprising passing a laser beam through an optical crystal made of the compound of claim 1.

11. An optical device comprising an optical crystal made of the compound of claim 1, wherein the optical device is a harmonic generator, an optical parametric amplifier, or an optical waveguide.

12. The compound of claim 4, wherein the nonlinear optical crystal of potassium lithium monohydrogen cyanurate dihydrate has an X-ray powder diffraction pattern as shown in FIG. 3.

13. The compound of claim 4, wherein the nonlinear optical crystal of potassium lithium monohydrogen cyanurate dihydrate does not have a symmetry center, and belongs to an orthorhombic crystal system, having space group Pna2(1) and cell parameters a=15.387(6) , b=3.6524(16) , c=12.755(6) , ===90, Z=4, and a unit cell volume V=716.82 .sup.3.

14. The compound as claimed in claim 5, wherein the nonlinear optical crystal of rubidium lithium monohydrogen cyanurate dihydrate has an X-ray powder diffraction pattern as shown in FIG. 4.

15. The compound as claimed in claim 5, wherein the nonlinear optical crystal of rubidium lithium monohydrogen cyanurate dihydrate does not have a symmetry center, and belongs to an orthorhombic crystal system, having space group Pna2(1), cell parameters a=15.682(7) , b=3.7453(17) , c=12.768(6) , ===90, Z=4, and a unit cell volume V=749.9 .sup.3.

16. The compound of claim 6, wherein the nonlinear optical crystal of rubidium sodium monohydrogen cyanurate dihydrate has an X-ray powder diffraction pattern as shown in FIG. 5.

17. The compound of claim 6, wherein the nonlinear optical crystal of rubidium sodium monohydrogen cyanurate dihydrate does not have a symmetry center, and belongs to an orthorhombic crystal system, having space group Pna2(1), cell parameters =15.829(18) , b=3.964(5) , c=13.068(16) , ===90, Z=4, and a unit cell volume V=819.8 .sup.3.

18. The method of claim 8, wherein the reaction is carried out in an organic solvent or an inorganic solvent; and/or the reaction is carried out at a temperature of 50-110 C.

19. The method of claim 9, wherein: the cooling rate is in a range of 1-10 C./hour; and/or the reaction liquid is cooled to 0-40 C.; and/or the alkali metal monohydrogen cyanurate compound is washed with water, acetone, or a mixture thereof.

Description

DESCRIPTION OF FIGURES

(1) 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.

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

(3) FIG. 3 is the X-ray diffraction pattern of KLHCY single crystal after grinding into powder.

(4) FIG. 4 is the X-ray diffraction pattern of RLHCY single crystal after grinding into powder.

(5) FIG. 5 is the X-ray diffraction pattern of RNHCY single crystal after grinding into powder.

SPECIFIC MODE FOR CARRYING OUT THE INVENTION

(6) 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).Math.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.

(7) 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.

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

(9) Raw materials used for the preparation of KLi(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O single crystal: KOH 3.44 g (0.06 mol) LiOH.Math.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

(10) 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).Math.2H.sub.2O single crystal with a size of 511 mm.

(11) Raw materials used for the preparation of RbLi(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O single crystal: RbOH.Math.H.sub.2O 7.23 g (0.06 mol) LiOH.Math.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

(12) 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).Math.2H.sub.2O single crystal with a size of 115 mm.

(13) Raw materials used for the preparation of RbNa(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O single crystal: NaOH 2.40 g (0.06 mol) RbOH.Math.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

(14) 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).Math.2H.sub.2O single crystal with a size of 151 mm.

EXAMPLE 2

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

(15) Raw materials used for the preparation of KLi(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O single crystal: KOH 3.44 g (0.06 mol) LiOH.Math.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

(16) 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).Math.2H.sub.2O single crystal with a size of 522 mm.

(17) Raw materials used for the preparation of RbLi(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O single crystal: RbOH.Math.H.sub.2O 7.23 g (0.06 mol) LiOH.Math.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

(18) 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).Math.2H.sub.2O single crystal with a size of 225 mm.

(19) Raw materials used for the preparation of RbNa(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O single crystal: NaOH 2.40 g (0.06 mol) RbOH.Math.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

(20) 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).Math.2H.sub.2O single crystal with a size of 252 mm.

EXAMPLE 3

(21) The KLi(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O, RbLi(HC.sub.3N.sub.3O.sub.3).Math.2H.sub.2O and RbNa(HC.sub.3N.sub.3O.sub.3).Math.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).Math.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).Math.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).Math.2H.sub.2O crystal was about 2 times that of KDP under the equal conditions.

(22) 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.