Dihydroguanidino urea phosphite nonlinear optical crystal as well as preparation method and application thereof

Abstract

The invention relates to a dihydroguanidino urea phosphite nonlinear optical crystal as well as a preparation method and application thereof. The molecular formula of the crystal is (C2N4OH7) H2PO3, the molecular weight is 184.1, the crystal belongs to a monoclinic system, the space group is Cc, and the cell parameters are as follows: a = 6.698 (1), b = 6.8396 (10), c = 16.350 (3), alpha = 90.00 degrees, beta = 96.500 (6) degrees, gamma = 90.00 degrees, Z = 4 and V = 744.2 (2) 3. Crystals with the size of more than centimeter level are grown by adopting an evaporation method, an aqueous solution cooling method, a hydrothermal method or a solvothermal method. Under the irradiation of 1064nm laser, the powder frequency-doubled effect of the crystal is about 4-5 times that of KH2PO4 (KDP), the ultraviolet absorption edge of the crystal is about 215nm, the experimental birefringence is about 0.19 at-589.3 nm, and birefringence phase matching within the lowest transmission range can be theoretically realized. The crystal is simple in preparation method and low in cost, has a relatively large nonlinear optical effect, a relatively large birefringence and a wide transmission range, is easy to grow and process, and can be used as an ultraviolet nonlinear optical crystal and a birefringence crystal.

Description

Technical Field

[0001] The invention relates to a nonlinear optical crystal of dihydroguanidinyl phosphite and a preparation method and application thereof. Background Art

[0002] Ultraviolet (UV) or deep ultraviolet (DUV) nonlinear optical (NLO) materials play an important role in laser frequency conversion, lithography, semiconductor lithography, etc. Due to the ability to generate coherent UV or DUV light, scientists have invented some UV and DUV band NLO crystals in the past few decades, including β-BaB 2 O 4 (BBO), LiB 3 O 5 (LBO), CsB 3 O 5 (CBO), CsLiB 6 O 10 (CLBO), KBe 2 BO 3 F 2 (KBBF), K 3 B 6 O 10 Cl(KBOC), etc. As we all know, the only practical deep ultraviolet nonlinear optical crystal is the (KBBF) crystal invented by Chinese scientists. This crystal has a layered growth habit, and it is difficult to grow large-sized crystals, which limits its application to a certain extent. Scientists from all over the world are still paying close attention to the exploration and research of various new types of nonlinear optical crystals, not only focusing on the optical and mechanical properties of the crystals, but also paying more and more attention to the preparation characteristics of the crystals.

[0003] In the previous research, the present invention invented the compound barium fluoroborate and barium fluoroborate nonlinear optical crystal and preparation method and use thereof (patent application number: 2011102581710), the compound ammonium fluoroborate NH 4 B 4 O 6 F and ammonium fluoroborate NH 4 B 4 O 6 F nonlinear optical crystal (patent application number: 2016111282833), compound rubidium fluoroborate and rubidium fluoroborate nonlinear optical crystal and preparation method and use (patent application number: 2017102153471), compound cesium fluoroborate and cesium fluoroborate nonlinear optical crystal and preparation method and use (patent application number: 2017102153378), guanidine tetrafluoroborate nonlinear optical crystal and preparation method and use (patent application number: 2020115685331) and other related patents.

[0004] The main difference between the present invention and the above patents is that the isolated guanidinium ions and the isolated dihydrogen phosphite ions in dihydrogen guanidinyl urea phosphite are connected by hydrogen bonds, and the bonding forces of the structures are different, resulting in completely different structures and growth habits. In addition, dihydrogen guanidinyl urea phosphite can be stably grown by a simple solvothermal method, the crystal quality is high, the cost is very low, and the key parameters of the growth process and the crystal properties are different from those of previous crystals. Summary of the invention

[0005] The object of the present invention is to provide a nonlinear optical crystal of dihydroguanidinyl urea phosphite, the chemical formula of which is (C 2 N 4 OH 7 )H 2 PO 3 , molecular weight is 184.1, belongs to monoclinic system, space group is Cc, unit cell parameters are α=90.00°, β=96.500(6)°, γ=90.00°, Z=4,

[0006] Another object of the present invention is to provide a method for preparing a nonlinear optical crystal of dihydroguanidinyl urea phosphite, wherein the crystal is grown by evaporation, aqueous solution cooling, hydrothermal or solvothermal method.

[0007] Another object of the present invention is to provide a use of guanidinyl urea phosphite nonlinear optical crystal.

[0008] The present invention discloses a nonlinear optical crystal of dihydroguanidinyl urea phosphite, the chemical formula of which is (C 2 N 4 OH 7 )H 2 PO 3 , molecular weight is 184.1, belongs to monoclinic system, space group is Cc, unit cell parameters are α=90.00°, β=96.500(6)°, γ=90.00°, Z=4,

[0009] The method for preparing the dihydroguanidinourea phosphite nonlinear optical crystal adopts an evaporation method, an aqueous solution cooling method, a hydrothermal method or a solvothermal method to grow the crystal;

[0010] The specific operation of growing the dihydroguanidino urea phosphite nonlinear optical crystal by the evaporation method is carried out in the following steps:

[0011] a. molar ratio [C 2 N 4 OH 7]∶P=1∶0.8-1.2 will contain [C 2 N 4 OH 7 ] compound and the P-containing compound are mixed evenly, 20-100 ml of deionized water is added to mix, a mixed solution is obtained, and then ultrasonic treatment is performed to fully mix and dissolve the mixture to obtain a clear solution; the compound containing [C 2 N 4 OH 7 ]Compound C 4 H 12 N 8 O 2 ·H 2 SO 4 , C 4 H 12 N 8 O 2 ·H 2 CO 3 , C 2 N 4 OH 6 HCl or C 2 N 4 OH 6 ·HNO 3 ; Compounds containing P are H 3 PO 3 , KH 2 PO 3 , Ca(H 2 PO 3 ) 2 OrBa(H 2 PO 3 ) 2 ;

[0012] or in molar ratio [C 2 N 4 OH 7 ]∶P=1∶0.8-1.2 will contain [C 2 N 4 H 4 ] compound and P-containing compound are mixed evenly, 20-100 ml of deionized water and 0-10 ml of protonic acid solution are added to mix, and then 0-10 ml of alkali solution is added to obtain a mixed solution, and then ultrasonic treatment is performed to fully mix and dissolve it to obtain a clear solution; the compound containing [C 2 N 4 H 4 The compound is C 2 N 4 H 4 (Cyanoguanidine) organic substance; compound containing P is H 3 PO 3 , KH 2 PO3 , Ca(H 2 PO 3 ) 2 OrBa(H 2 PO 3 ) 2 ; Protonic acid solution is H 2 SO 4 or HNO 3 ; The alkaline solution is KOH;

[0013] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 20-85°C at a rate of 5-15°C / h, keep the temperature constant for 7-14 days to evaporate the solvent, and wait until the crystal growth is completed to obtain a guanidino urea phosphite nonlinear optical crystal;

[0014] The aqueous solution cooling method for growing the diguanidino urea phosphite nonlinear optical crystal is specifically performed in the following steps:

[0015] a. molar ratio [C 2 N 4 OH 7 ]∶P=1∶0.8-1.2 will contain [C 2 N 4 OH 7 ] compound and the P-containing compound are mixed evenly, 20-100 ml of deionized water is added to mix, a mixed solution is obtained, and then ultrasonic treatment is performed to fully mix and dissolve the mixture to obtain a clear solution; the compound containing [C 2 N 4 OH 7 ]Compound C 4 H 12 N 8 O 2 ·H 2 SO 4 , C 4 H 12 N 8 O 2 ·H 2 CO 3 , C 2 N 4 OH 6 HCl or C 2 N 4 OH 6 ·HNO 3 ; Compounds containing P are H 3 PO 3 , KH 2 PO 3 , Ca(H 2 PO 3 ) 2 OrBa(H 2PO 3 ) 2 ;

[0016] Or in molar ratio [C 2 N 4 OH 7 ]∶P=1∶0.8-1.2 will contain [C 2 N 4 H 4 ] compound and P-containing compound are mixed evenly, 20-100 ml of deionized water and 0-10 ml of protonic acid solution are added to mix, and then 0-10 ml of alkali solution is added to obtain a mixed solution, and then ultrasonic treatment is performed to fully mix and dissolve it to obtain a clear solution; the compound containing [C 2 N 4 H 4 ]Compound C 2 N 4 H 4 (Cyanoguanidine) organic substance; compound containing P is H 3 PO 3 , KH 2 PO 3 , Ca(H 2 PO 3 ) 2 OrBa(H 2 PO 3 ) 2 ; Protonic acid solution is H 2 SO 4 , HNO 3 , H 3 PO 4 or HF; the alkaline solution is KOH, NaOH, Ca(OH) 2 or Ba(OH) 2 ;

[0017] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 20-85°C at a rate of 5-15°C / h, keep the temperature constant for 3-7 days until the solution evaporates to saturation, and then cool it down to room temperature at a rate of 0.1-1°C / d to obtain a hydroxyphosphite aminoguanidine nonlinear optical crystal;

[0018] The hydrothermal method for growing the diguanidinyl urea phosphite nonlinear optical crystal is specifically performed in the following steps:

[0019] a. molar ratio [C 2 N 4 OH 7 ]∶P=1∶0.8-1.2 will contain [C 2 N 4 OH 7] compound and the P-containing compound are mixed evenly, 5-10 ml of deionized water is added to mix, a mixed solution is obtained, and then ultrasonic treatment is performed to fully mix and dissolve the mixture to obtain a clear solution; the compound containing [C 2 N 4 OH 7 The compound is C 4 H 12 N 8 O 2 ·H 2 SO 4 , C 4 H 12 N 8 O 2 ·H 2 CO 3 , C 2 N 4 OH 6 HCl or C 2 N 4 OH 6 ·HNO 3 ; Compounds containing P are H 3 PO 3 , KH 2 PO 3 , Ca(H 2 PO 3 ) 2 OrBa(H 2 PO 3 ) 2 ;

[0020] b. Transfer the mixed solution in step a into a polytetrafluoroethylene liner of a hydrothermal reactor with a volume of 23-100 ml, and tighten and seal the reactor; then heat it to 50-200°C at a rate of 10-20°C / h, keep it at a constant temperature for 2-5 days, and then cool it to room temperature at a rate of 1-2°C / h to obtain a dihydroguanidinyl urea nonlinear optical crystal;

[0021] The solvothermal method for growing the dihydroguanidino urea phosphite nonlinear optical crystal is specifically performed in the following steps:

[0022] a. molar ratio [C 2 N 4 OH 7 ]∶P=1∶0.8-1.2 will contain [C 2 N 4 OH 7 ] compound and the P-containing compound are mixed evenly, 20-100 ml of a mixture of deionized water and an organic solvent are added to obtain a mixed solution, and then ultrasonic treatment is performed to fully mix and dissolve the mixed solution to obtain a clear solution; the compound containing [C 2 N 4OH 7 ]Compound C 4 H 12 N 8 O 2 ·H 2 SO 4 , C 4 H 12 N 8 O 2 ·H 2 CO 3 , C 2 N 4 OH 6 HCl or C 2 N 4 OH 6 ·HNO 3 ; Compounds containing P are H 3 PO 3 , KH 2 PO 3 , Ca(H 2 PO 3 ) 2 OrBa(H 2 PO 3 ) 2 ;

[0023] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 20-85°C at a rate of 5-15°C / h, keep the temperature constant for 7-14 days to evaporate the solvent, and wait until the crystal growth is completed to obtain a guanidino urea phosphite nonlinear optical crystal;

[0024] The dihydroguanidinyl urea phosphite nonlinear optical crystal is used in preparing harmonic light output of 1064nm fundamental frequency light output by Nd:YAG laser for frequency doubling, tripling, quadrupling and quintuple doubling.

[0025] The dihydroguanidinyl urea phosphite nonlinear optical crystal is used in preparing ultraviolet frequency-doubled light output at or below 266 nm.

[0026] The guanidinyl urea phosphite nonlinear optical crystal is used in preparing a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

[0027] The preparation method of the guanidino urea phosphite nonlinear optical crystal of the present invention comprises the following containers used in the preparation process: a glass beaker, a ceramic beaker, a polytetrafluoroethylene beaker, a polytetrafluoroethylene pressure autoclave liner, a stainless steel autoclave, a polymethyl methacrylate container, and a conical flask; when the container is a conical flask or a beaker, the container must be cleaned with acid first, then rinsed with deionized water, and dried.

[0028] In the preparation method of the dihydroguanidino urea phosphite nonlinear optical crystal of the present invention, the resistance furnace used in the preparation process is a temperature-controlled water bath pot, a muffle furnace or a drying box.

[0029] The preparation method of the dihydroguanidinyl phosphite nonlinear optical crystal of the present invention is adopted to obtain a dihydroguanidinyl phosphite nonlinear optical crystal with a size of centimeters. By using a large-sized container and extending the growth period of the crystal, a corresponding large-sized nonlinear optical crystal dihydroguanidinyl phosphite can be obtained. During the growth of the dihydroguanidinyl phosphite nonlinear optical crystal, the crystal is easy to grow, transparent and without wrapping, and has the advantages of fast growth speed, low cost, easy acquisition of large-sized crystals, etc.

[0030] The dihydroguanidinyl urea nonlinear optical crystal obtained by the preparation method of the dihydroguanidinyl urea phosphite nonlinear optical crystal of the present invention can be used as a nonlinear optical device by orienting the crystal blank according to the crystallographic data of the crystal, cutting the crystal according to the required angle, thickness and cross-sectional size, and polishing the light-transmitting surface of the crystal. The dihydroguanidinyl urea nonlinear optical crystal has the advantages of a light transmission band reaching the ultraviolet region, stable physical and chemical properties, not easy to deliquesce, easy to process and store, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The calculated and experimental powder XRD spectra of the compound dihydroguanidino urea phosphite of the present invention;

[0032] Figure 2 The morphology of the dihydroguanidinourea phosphite crystals of the present invention;

[0033] Figure 3 This is a structural diagram of the dihydroguanidinourea phosphite crystal of the present invention;

[0034] Figure 4 This is a working principle diagram of a nonlinear optical device made of the dihydroguanidinyl phosphite crystal of the present invention, wherein 1 is a laser, 2 is an emitted light beam, 3 is the dihydroguanidinyl phosphite crystal, 4 is an output light beam, and 5 is a filter. DETAILED DESCRIPTION

[0035] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. The following shall not be used as a limitation on the scope of protection of the present invention, and any improvements made on the basis of the present invention shall not violate the spirit of the present invention. The raw materials or equipment used in the present invention, unless otherwise specified, are all commercially available.

[0036] Example 1

[0037] According to the reaction formula: C 4 H 12 N 8 O 2 ·H2 SO 4 +2H 3 PO 3 +Ba(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +BaSO 4 +2H 2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0038] a. Add C in a molar ratio of 1:2:1 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ba(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0039] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 7 mm×3 mm×3 mm is obtained.

[0040] Example 2

[0041] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +Ba(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +BaSO 4 +2H 2 O, grown by evaporation (C 2 N 4 OH 7)H 2 PO 3 Nonlinear optical crystals:

[0042] a. C in a molar ratio of 1:1.6:0.8 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ba(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0043] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 7 mm×4 mm×3 mm is obtained.

[0044] Example 3

[0045] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +Ba(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +BaSO 4 +2H 2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0046] a. C in a molar ratio of 1:2.4:1.2 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ba(OH) 2Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0047] b. Place the clarified solution in step a in a resistance furnace, heat it to 30°C at a rate of 10°C / h, keep it at a constant temperature for 14 days to evaporate the solvent, and wait until the crystal growth is completed to obtain a 7mm×4mm×3mm dihydroguanidinyl urea nonlinear optical crystal.

[0048] Example 4

[0049] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +Ca(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +CaSO 4 +2H 2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0050] a. Add C in a molar ratio of 1:2:1 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ca(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0051] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 6 mm×3 mm×2 mm is obtained.

[0052] Example 5

[0053] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +Ca(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +CaSO 4 +2H 2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0054] a. C in a molar ratio of 1:1.6:0.8 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ca(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0055] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a 6 mm×3 mm×3 mm nonlinear optical crystal of dihydroguanidinyl urea phosphite is obtained.

[0056] Example 6

[0057] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +Ca(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +CaSO4 +2H 2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0058] a. C in a molar ratio of 1:2.4:1.2 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ca(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0059] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 6 mm×5 mm×2 mm is obtained.

[0060] Example 7

[0061] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +2KOH→2(C 2 N 4 OH 7 )H 2 PO 3 +K 2 SO 4 +2H 2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0062] a. Add C in a molar ratio of 1:2:2 4 H 12 N 8 O 2 ·H 2 SO4 , H 3 PO 3 Mix well with KOH, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0063] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of dihydroguanidinyl urea phosphite with a size of 11 mm×4 mm×2 mm is obtained.

[0064] Example 8

[0065] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +2KOH→2(C 2 N 4 OH 7 )H 2 PO 3 +K 2 SO 4 +2H 2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0066] a. C in a molar ratio of 1:1.6:1.6 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 Mix well with KOH, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0067] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 11 mm×6 mm×2 mm is obtained.

[0068] Example 9

[0069] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +2KOH→2(C 2 N 4 OH 7 )H 2 PO 3 +K 2 SO 4 +2H 2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0070] a. Mix C in a molar ratio of 1:2.4:2.4 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 Mix well with KOH, put into a 200ml polytetrafluoroethylene beaker, add 100ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0071] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 10 mm×5 mm×2 mm is obtained.

[0072] Example 10

[0073] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 CO 3 +2H 3 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +CO 2 +H2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0074] a. Add C in a molar ratio of 1:2 4 H 12 N 8 O 2 ·H 2 CO 3 and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0075] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 12 mm×7 mm×2 mm is obtained.

[0076] Embodiment 11

[0077] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 CO 3 +2H 3 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +CO 2 +H 2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0078] a. C in a molar ratio of 1:1.6 4 H 12 N 8 O 2 ·H 2 CO 3 and H 3 PO 3Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0079] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a guanidinyl urea phosphite nonlinear optical crystal with a size of 12 mm×6 mm×2 mm is obtained.

[0080] Example 12

[0081] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 CO 3 +2H 3 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +CO 2 +H 2 O, grown by evaporation (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0082] a. C in a molar ratio of 1:2.4 4 H 12 N 8 O 2 ·H 2 CO 3 and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0083] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 13 mm×7 mm×2 mm is obtained.

[0084] Embodiment 13

[0085] According to the reaction formula: C 2 N 4 H4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by evaporation method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0086] a. Add C in a molar ratio of 1:1 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0087] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 10 mm×5 mm×3 mm is obtained.

[0088] Embodiment 14

[0089] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by evaporation method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0090] a. C in a molar ratio of 1:0.8 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3Mix well, put into a 20 ml polytetrafluoroethylene beaker, add 100 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0091] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 10 mm×5 mm×5 mm is obtained.

[0092] Embodiment 15

[0093] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by evaporation method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0094] a. C in a molar ratio of 1:1.2 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml of deionized water, stir well to obtain a mixed solution, and then treat with ultrasound to mix it well to obtain a clear solution;

[0095] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 9 mm×5 mm×4 mm is obtained.

[0096] Example 16

[0097] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +HNO 3 +KOH→(C 2 N 4 OH 7)H 2 PO 3 +KNO 3 , grown by evaporation method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0098] a. Add C in a molar ratio of 1:1 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 The mixture was mixed evenly, and then placed in a 200 ml polytetrafluoroethylene beaker, 50 ml of deionized water was added, and then 10 ml of nitric acid solution was added, and stirred evenly to obtain a mixed solution, and then ultrasonic treatment was performed to mix the mixture well to obtain a clear solution; then KOH in an amount equal to the molar amount of nitric acid was added to the clear solution, and stirred evenly to obtain a mixed solution;

[0099] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 17 mm×8 mm×6 mm is obtained.

[0100] Embodiment 17

[0101] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +HNO 3 +KOH→(C 2 N 4 OH 7 )H 2 PO 3 +KNO 3 , grown by evaporation method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0102] a. C in a molar ratio of 1:0.8 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml deionized water, then add 8 ml nitric acid solution, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution; then add KOH in an amount equal to the molar amount of nitric acid to the clear solution, stir well to obtain a mixed solution;

[0103] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 11 mm×6 mm×2 mm is obtained.

[0104] Embodiment 18

[0105] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +HNO 3 +KOH→(C 2 N 4 OH 7 )H 2 PO 3 +KNO 3 , grown by evaporation method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0106] a. C in a molar ratio of 1:1.2 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml deionized water, then add 5 ml nitric acid solution, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution; then add KOH in an amount equal to the molar amount of nitric acid to the clear solution, stir well to obtain a mixed solution;

[0107] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 14 mm×7 mm×4 mm is obtained.

[0108] Embodiment 19

[0109] According to the reaction formula: 2C 2 N 4 H4 +H 2 SO 4 +2KH 2 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +K 2 SO 4 , grown by evaporation method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0110] a. Add C in a molar ratio of 1:1 2 N 4 H 4 (Cyanoguanidine) and KH 2 PO 3 Mix well, put into a 200ml polytetrafluoroethylene beaker, add 50ml deionized water, and then add 1ml H 2 SO 4 The solution is stirred evenly to obtain a mixed solution; and then subjected to ultrasonic treatment to fully mix the solution to obtain a clear solution;

[0111] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 17 mm×8 mm×6 mm is obtained.

[0112] Embodiment 20

[0113] According to the reaction formula: 2C 2 N 4 H 4 +H 2 SO 4 +2KH 2 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +K 2 SO 4 , grown by evaporation method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0114] a. C in a molar ratio of 1:0.8 2 N 4 H 4 (Cyanoguanidine) and KH 2 PO 3 Mix well, put into a 200ml polytetrafluoroethylene beaker, add 20ml deionized water, and then add 10ml H 2 SO 4 The solution is stirred evenly to obtain a mixed solution; and then subjected to ultrasonic treatment to fully mix the solution to obtain a clear solution;

[0115] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a guanidinyl urea phosphite nonlinear optical crystal with a size of 11 mm×7 mm×6 mm is obtained.

[0116] Embodiment 21

[0117] According to the reaction formula: 2C 2 N 4 H 4 +H 2 SO 4 +2KH 2 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +K 2 SO 4 , grown by evaporation method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0118] a. C in a molar ratio of 1:1.2 2 N 4 H 4 (Cyanoguanidine) and KH 2 PO 3 Mix well, put into a 200ml polytetrafluoroethylene beaker, add 100ml deionized water, and then add 5ml H 2 SO 4 The solution is stirred evenly to obtain a mixed solution; and then subjected to ultrasonic treatment to fully mix the solution to obtain a clear solution;

[0119] b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 30° C. at a rate of 10° C. / h, and keep the temperature constant for 14 days to evaporate the solvent. When the crystal growth is completed, a nonlinear optical crystal of guanidinyl phosphite with a size of 13 mm×6 mm×6 mm is obtained.

[0120] Embodiment 22

[0121] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +Ba(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +BaSO 4 +2H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0122] a. Add C in a molar ratio of 1:2:1 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ba(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0123] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 17 mm×5 mm×4 mm.

[0124] Embodiment 23

[0125] According to the reaction formula: C 4 H 12 N 8 O 2 ·H2 SO 4 +2H 3 PO 3 +Ba(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +BaSO 4 +2H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0126] a. C in a molar ratio of 1:1.6:0.8 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ba(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0127] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 14 mm×5 mm×2 m.

[0128] Embodiment 24

[0129] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +Ba(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +BaSO 4 +2H 2 O, grown by cooling method using aqueous solution (C 2 N4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0130] a. C in a molar ratio of 1:2.4:1.2 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ba(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0131] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 12 mm×5 mm×5 mm.

[0132] Embodiment 25

[0133] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +Ca(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +CaSO 4 +2H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0134] a. Add C in a molar ratio of 1:2:1 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO3 and Ca(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0135] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 8 mm×5 mm×4 mm.

[0136] Embodiment 26

[0137] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +Ca(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +CaSO 4 +2H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0138] a. Add C in a molar ratio of 1:1.6:1 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ca(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0139] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidinyl phosphite nonlinear optical crystal with a size of 14 mm×7 mm×3 mm.

[0140] Embodiment 27

[0141] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +Ca(OH) 2 →2(C 2 N 4 OH 7 )H 2 PO 3 +CaSO 4 +2H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0142] a. C in a molar ratio of 1:2.4:1.2 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 and Ca(OH) 2 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve, filter to obtain a clear solution;

[0143] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 12 mm×8 mm×4 mm.

[0144] Embodiment 28

[0145] According to the reaction formula: C 4 H 12 N 8 O2 ·H 2 SO 4 +2H 3 PO 3 +2KOH→2(C 2 N 4 OH 7 )H 2 PO 3 +K 2 SO 4 +2H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0146] a. Add C in a molar ratio of 1:2:2 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 Mix well with KOH, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0147] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 12 mm×6 mm×4 mm.

[0148] Embodiment 29

[0149] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +2KOH→2(C 2 N 4 OH 7 )H 2 PO 3 +K 2 SO 4 +2H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH7 )H 2 PO 3 Nonlinear optical crystals:

[0150] a. C in a molar ratio of 1:1.6:1.6 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3 Mix well with KOH, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0151] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 9 mm×6 mm×3 mm.

[0152] Embodiment 30

[0153] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 SO 4 +2H 3 PO 3 +2KOH→2(C 2 N 4 OH 7 )H 2 PO 3 +K 2 SO 4 +2H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0154] a. Mix C in a molar ratio of 1:2.4:2.4 4 H 12 N 8 O 2 ·H 2 SO 4 , H 3 PO 3Mix well with KOH, put into a 200ml polytetrafluoroethylene beaker, add 100ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0155] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 13 mm×5 mm×3 mm.

[0156] Embodiment 31

[0157] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 CO 3 +2H 3 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +CO 2 +H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0158] a. Add C in a molar ratio of 1:2 4 H 12 N 8 O 2 ·H 2 CO 3 and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0159] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 7 mm×6 mm×2 mm.

[0160] Embodiment 32

[0161] According to the reaction formula: C4 H 12 N 8 O 2 ·H 2 CO 3 +2H 3 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +CO 2 +H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0162] a. C in a molar ratio of 1:1.6 4 H 12 N 8 O 2 ·H 2 CO 3 and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0163] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a 9mm×4mm×2mm nonlinear optical crystal of dihydroguanidinyl urea phosphite.

[0164] Embodiment 33

[0165] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 CO 3 +2H 3 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +CO 2 +H 2 O, grown by cooling method using aqueous solution (C 2 N 4 OH7 )H 2 PO 3 Nonlinear optical crystals:

[0166] a. C in a molar ratio of 1:2.4 4 H 12 N 8 O 2 ·H 2 CO 3 and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to fully mix and dissolve to obtain a clear solution;

[0167] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 7 mm×5 mm×2 mm.

[0168] Embodiment 34

[0169] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , using aqueous solution cooling method to grow (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0170] a. Add C in a molar ratio of 1:1 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0171] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 11 mm×9 mm×5 mm.

[0172] Embodiment 35

[0173] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , using aqueous solution cooling method to grow (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0174] a. C in a molar ratio of 1:0.8 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml of deionized water, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0175] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 0.5°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 11 mm×9 mm×5 mm.

[0176] Embodiment 36

[0177] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , using aqueous solution cooling method to grow (C 2 N4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0178] a. C in a molar ratio of 1:1.2 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml deionized water, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0179] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidinyl phosphite nonlinear optical crystal with a size of 13 mm×4 mm×4 mm.

[0180] Embodiment 37

[0181] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +HNO 3 +KOH→(C 2 N 4 OH 7 )H 2 PO 3 +KNO 3 , using aqueous solution cooling method to grow (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0182] a. Add C in a molar ratio of 1:1 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 The mixture was mixed evenly, and then placed in a 200 ml polytetrafluoroethylene beaker, 50 ml of deionized water was added, and then 10 ml of nitric acid solution was added, and stirred evenly to obtain a mixed solution; then the mixture was subjected to ultrasonic treatment to be fully mixed to obtain a clear solution; then KOH in an amount equal to the molar amount of the added nitric acid was added to the clear solution, and stirred evenly to obtain a mixed solution;

[0183] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 7 mm×5 mm×4 mm.

[0184] Embodiment 38

[0185] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +HNO 3 +KOH→(C 2 N 4 OH 7 )H 2 PO 3 +KNO 3 , using aqueous solution cooling method to grow (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0186] a. C in a molar ratio of 1:0.8 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml of deionized water, then add 1 ml of the solution, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution; then add KOH in an amount equal to the molar amount of the added nitric acid to the clear solution, stir well to obtain a mixed solution;

[0187] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 1°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 12 mm×6 mm×1 mm.

[0188] Embodiment 39

[0189] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +HNO 3 +KOH→(C 2 N 4 OH 7)H 2 PO 3 +KNO 3 , using aqueous solution cooling method to grow (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0190] a. C in a molar ratio of 1:1.2 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml deionized water, then add 5 ml nitric acid solution, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution; then add KOH in an amount equal to the molar amount of the added nitric acid to the clear solution, stir well to obtain a mixed solution;

[0191] b. Place the clarified solution in step a in a resistance furnace, heat it to 60°C at a rate of 10°C / h, keep it at a constant temperature to evaporate the solvent until the solution is saturated, seal the container, and cool it to 20°C at a rate of 0.5°C / d to obtain a guanidino urea phosphite nonlinear optical crystal with a size of 11 mm×10 mm×6 mm.

[0192] Embodiment 40

[0193] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +HNO 3 +KOH→(C 2 N 4 OH 7 )H 2 PO 3 +KNO 3 , grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0194] a. In a molar ratio of 1:1:1: 2 N 4 H 4 (Cyanoguanidine), H 3 PO 3 , HNO 3and KOH, and add 7 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution, and then treat it with ultrasound to mix and dissolve them thoroughly to obtain a clear solution;

[0195] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a hydrothermal reactor with a volume of 23 ml, and tighten and seal the reactor. Then heat it to 150°C at a rate of 20°C / h, keep it at a constant temperature for 5 days, and then cool it to room temperature at a rate of 1°C / h. Open the high-pressure reactor, and obtain a nonlinear optical crystal of dihydroguanidin phosphite with a size of 16×7×5 mm in the colorless clear solution.

[0196] Embodiment 41

[0197] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +HNO 3 +KOH→(C 2 N 4 OH 7 )H 2 PO 3 +KNO 3 , grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0198] a. In a molar ratio of 1:0.8:0.8:0.8, C 2 N 4 H 4 (Cyanoguanidine), H 3 PO 3 , HNO 3 and KOH, and add 5 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution, and then treat it with ultrasound to mix and dissolve them thoroughly to obtain a clear solution;

[0199] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 50 mL autoclave, and seal the autoclave mouth tightly. Place the autoclave in a constant temperature box, and then heat it to 50°C at a rate of 10°C / h, keep the temperature constant for 2 days, and then cool it to room temperature at a rate of 2°C / day. Open the autoclave, and obtain a nonlinear optical crystal of dihydroguanidin phosphite with a size of 13×7×6 mm in the colorless clear solution.

[0200] Embodiment 42

[0201] According to the reaction formula: C 2N 4 H 4 +H 3 PO 3 +HNO 3 +KOH→(C 2 N 4 OH 7 )H 2 PO 3 +KNO 3 , grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0202] a. Mix C in a molar ratio of 1:1.2:1.2:1.2 2 N 4 H 4 (Cyanoguanidine), H 3 PO 3 , HNO 3 and KOH, and add 10 mL of deionized water to mix and dissolve them thoroughly to obtain a mixed solution, and then treat it with ultrasound to mix and dissolve them thoroughly to obtain a clear solution;

[0203] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 75 mL autoclave, and seal the autoclave mouth tightly. Place the autoclave in a constant temperature box, raise the temperature to 100°C at a rate of 15°C / h, keep the temperature constant for 3 days, and then cool to room temperature at a rate of 2°C / day. Open the autoclave, and obtain a nonlinear optical crystal of dihydroguanidin phosphite with a size of 14×5×4 mm in the colorless clear solution.

[0204] Embodiment 43

[0205] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0206] a. Add C in a molar ratio of 1:1 2 N4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, add 7 mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution, and then treat with ultrasound to mix and dissolve thoroughly to obtain a clear solution;

[0207] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 100 mL autoclave, and seal the autoclave mouth tightly. Place the autoclave in a constant temperature box, heat it to 130°C at a rate of 12°C / h, keep the temperature constant for 4 days, and then cool it to room temperature at a rate of 1°C / day. Open the autoclave, and obtain a nonlinear optical crystal of dihydroguanidin phosphite with a size of 15×5×6 mm in the colorless clear solution.

[0208] Embodiment 44

[0209] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0210] a. C in a molar ratio of 1:0.8 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, add 5 mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution, and then treat with ultrasound to mix and dissolve thoroughly to obtain a clear solution;

[0211] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 25 mL autoclave, and seal the autoclave mouth tightly. Place the autoclave in a constant temperature box, raise the temperature to 80°C at a rate of 15°C / h, keep the temperature constant for 5 days, and then cool to room temperature at a rate of 1°C / day. Open the autoclave, and obtain a nonlinear optical crystal of dihydroguanidin phosphite with a size of 15×5×5 mm in the colorless clear solution.

[0212] Embodiment 45

[0213] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0214] a. C in a molar ratio of 1:1.2 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, add 10 mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution, and then treat with ultrasound to mix and dissolve thoroughly to obtain a clear solution;

[0215] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 50 mL autoclave, and seal the autoclave mouth tightly. Place the autoclave in a constant temperature box, raise the temperature to 200°C at a rate of 10°C / h, keep the temperature constant for 2 days, and then cool to room temperature at a rate of 1°C / day. Open the autoclave, and obtain a nonlinear optical crystal of dihydroguanidin phosphite with a size of 13×4×4 mm in the colorless clear solution.

[0216] Embodiment 46

[0217] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 CO 3 +2H 3 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +CO 2 +H 2 O, grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0218] a. Add C in a molar ratio of 1:2 4 H 12 N 8 O 2 ·H 2 CO 3 and H 3 PO 3 Mix well, add 7 mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution, and then treat with ultrasound to mix and dissolve thoroughly to obtain a clear solution;

[0219] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 75 mL autoclave, and seal the autoclave mouth tightly. Place the autoclave in a constant temperature box, raise the temperature to 50°C at a rate of 12°C / h, keep the temperature constant for 5 days, and then cool to room temperature at a rate of 2°C / day. Open the autoclave, and obtain a nonlinear optical crystal of dihydroguanidinyl urea phosphite with a size of 7×5×4 mm in the colorless clear solution.

[0220] Embodiment 47

[0221] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 CO 3 +2H 3 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +CO 2 +H 2 O, grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0222] a. C in a molar ratio of 1:1.6 4 H 12 N 8 O 2 ·H 2 CO 3 and H 3 PO 3 Mix well, add 10 ml of deionized water to mix, obtain a mixed solution, and then treat it with ultrasound to make it fully mixed and dissolved to obtain a clear solution;

[0223] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 100 mL autoclave, and seal the autoclave mouth tightly. Place the autoclave in a constant temperature box, raise the temperature to 200°C at a rate of 20°C / h, keep the temperature constant for 3 days, and then cool it down to room temperature at a rate of 2°C / day. Open the autoclave, and obtain a nonlinear optical crystal of dihydroguanidinyl urea phosphite with a size of 7×4×3 mm in the colorless clear solution.

[0224] Embodiment 48

[0225] According to the reaction formula: C 4 H 12 N 8 O 2 ·H 2 CO 3 +2H 3 PO 3 →2(C 2 N 4 OH 7 )H 2 PO 3 +CO 2 +H 2 O, grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0226] a. C in a molar ratio of 1:2.4 4 H 12 N 8 O 2 ·H 2 CO 3 and H 3 PO 3 Mix well, add 10 mL of deionized water to mix and dissolve thoroughly to obtain a mixed solution, and then treat with ultrasound to mix and dissolve thoroughly to obtain a clear solution;

[0227] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 23 mL autoclave, and seal the autoclave mouth tightly. Place the autoclave in a constant temperature box, raise the temperature to 180°C at a rate of 18°C / h, keep the temperature constant for 4 days, and then cool to room temperature at a rate of 1°C / day. Open the autoclave, and obtain a nonlinear optical crystal of dihydroguanidinyl urea phosphite with a size of 10×5×4 mm in the colorless clear solution.

[0228] Embodiment 49

[0229] According to the reaction formula: C 2 N 4 OH6 ·HNO 3 +H 3 PO 3 →(C 2 N 4 OH 7 )H 2 PO 3 +NO 2 +H 2 O, grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0230] a. Add C in a molar ratio of 1:1 2 N 4 OH 7 ·HNO 3 and H 3 PO 3 Mix well, add 10 ml of deionized water to mix, obtain a mixed solution, and then treat it with ultrasound to make it fully mixed and dissolved to obtain a clear solution;

[0231] b. The mixed solution in step a was transferred into the polytetrafluoroethylene liner of an autoclave with a volume of 80 mL, and the mouth of the autoclave was screwed and sealed. The autoclave was placed in a constant temperature box, and the temperature was increased to 130° C. at a rate of 18° C. / h, and the temperature was kept constant for 4 days. Then the temperature was lowered to room temperature at a rate of 2° C. / day, and the autoclave was opened. A nonlinear optical crystal of dihydroguanidin phosphite with a size of 18×14×7 mm was obtained in the light brown clear solution.

[0232] Embodiment 50

[0233] According to the reaction formula: C 2 N 4 OH 6 ·HNO 3 +H 3 PO 3 →(C 2 N 4 OH 7 )H 2 PO 3 +NO 2 +H 2 O, grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0234] a. C in a molar ratio of 1:0.82 N 4 OH 7 ·HNO 3 and H 3 PO 3 Mix well, add 8 ml of deionized water to mix, obtain a mixed solution, and then treat it with ultrasound to make it fully mixed and dissolved to obtain a clear solution;

[0235] b. Transfer the mixed solution in step a into the polytetrafluoroethylene liner of a 70 mL autoclave, and tighten and seal the autoclave mouth. Place the autoclave in a constant temperature box, raise the temperature to 50° C. at a rate of 20° C. / h, keep the temperature constant for 2 days, and then cool to room temperature at a rate of 1° C. / day. Open the autoclave, and obtain a 9×8×7 mm nonlinear optical crystal of dihydroguanidin phosphite in the light brown clear solution.

[0236] Embodiment 51

[0237] According to the reaction formula: C 2 N 4 OH 6 ·HNO 3 +H 3 PO 3 →(C 2 N 4 OH 7 )H 2 PO 3 +NO 2 +H 2 O, grown by hydrothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0238] a. Add C in a molar ratio of 1:1 2 N 4 OH 7 ·HNO 3 and H 3 PO 3 Mix well, add 6 ml of deionized water to mix, obtain a mixed solution, and then treat it with ultrasound to make it fully mixed and dissolved to obtain a clear solution;

[0239] b. The mixed solution in step a was transferred into the polytetrafluoroethylene liner of a 40 mL autoclave, and the mouth of the autoclave was screwed and sealed. The autoclave was placed in a constant temperature box, and the temperature was increased to 60° C. at a rate of 12° C. / h, and the temperature was kept constant for 5 days. Then the temperature was lowered to room temperature at a rate of 1° C. / day, and the autoclave was opened. A nonlinear optical crystal of dihydroguanidin phosphite with a size of 13×11×7 mm was obtained in the light brown clear solution.

[0240] Embodiment 52

[0241] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by solvothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0242] a. Add C in a molar ratio of 1:1 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of acetonitrile aqueous solution, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0243] b. Place the clarified solution in step a at room temperature and keep it at a constant temperature for 14 days to evaporate the solvent. When crystal growth is completed, a guanidinyl urea phosphite nonlinear optical crystal with a size of 12 mm×6 mm×4 mm is obtained.

[0244] Embodiment 53

[0245] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by solvothermal method (C 2 N4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0246] a. C in a molar ratio of 1:0.8 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml of acetonitrile aqueous solution, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0247] b. Place the clarified solution in step a at room temperature and keep it at a constant temperature for 14 days to evaporate the solvent. When the crystal growth is completed, a guanidinyl urea phosphite nonlinear optical crystal with a size of 16 mm×7 mm×5 mm is obtained.

[0248] Embodiment 54

[0249] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by solvothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0250] a. C in a molar ratio of 1:1.2 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml acetonitrile aqueous solution, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0251] b. Place the clarified solution in step a at room temperature and keep it at a constant temperature for 14 days to evaporate the solvent. When crystal growth is completed, a guanidinyl urea phosphite nonlinear optical crystal with a size of 9 mm×5 mm×4 mm is obtained.

[0252] Embodiment 55

[0253] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by solvothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0254] a. Add C in a molar ratio of 1:1 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 50 ml of ethanol water solution, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0255] b. Place the clarified solution in step a at room temperature and keep it at a constant temperature for 14 days to evaporate the solvent. When crystal growth is completed, a guanidinyl urea phosphite nonlinear optical crystal with a size of 11 mm×9 mm×5 mm is obtained.

[0256] Embodiment 56

[0257] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by solvothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0258] a. C in a molar ratio of 1:0.8 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 20 ml of ethanol water solution, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0259] b. Place the clarified solution in step a at room temperature and keep it at a constant temperature for 14 days to evaporate the solvent. When the crystal growth is completed, a guanidinyl urea phosphite nonlinear optical crystal with a size of 11 mm×8 mm×4 mm is obtained.

[0260] Embodiment 57

[0261] According to the reaction formula: C 2 N 4 H 4 +H 3 PO 3 +H 2 O→(C 2 N 4 OH 7 )H 2 PO 3 , grown by solvothermal method (C 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals:

[0262] a. C in a molar ratio of 1:1.2 2 N 4 H 4 (Cyanoguanidine) and H 3 PO 3 Mix well, put into a 200 ml polytetrafluoroethylene beaker, add 100 ml ethanol aqueous solution, stir well to obtain a mixed solution; then treat with ultrasound to mix well to obtain a clear solution;

[0263] b. Place the clarified solution in step a at room temperature and keep it at a constant temperature for 14 days to evaporate the solvent. When the crystal growth is completed, a guanidinyl urea phosphite nonlinear optical crystal with a size of 12 mm×7 mm×3 mm is obtained.

[0264] Embodiment 58

[0265] Any (C) obtained in Example 1-57 2 N 4 OH 7 )H 2 PO 3 Nonlinear optical crystals are processed in matching directions and attached Figure 3As shown in the figure, it is placed at position 3, at room temperature, using a Q-switched Nd:YAG laser as the light source, the incident wavelength is 1064nm, and the infrared beam 2 with a wavelength of 1064nm emitted by the Q-switched Nd:YAG laser 1 is injected into (C 2 N 4 OH 7 )H 2 PO 3 Single crystal 3 produces green doubled-frequency light with a wavelength of 532nm, and its output intensity is about 3.0 times that of KDP under the same conditions. At the same time, under the same experimental device, it also produces purple doubled-frequency light with a wavelength of 266nm, and its output intensity is 0.7 times that of BBO under the same conditions.

Claims

1. A nonlinear optical crystal of dihydroguanidinyl phosphite, characterized in that The chemical formula of the crystal is (C2N4OH7)H2PO3, the molecular weight is 184.1, it belongs to the monoclinic system, and the space group is Cc , the unit cell parameters are a=6.698(1)Å, b=6.8396(10)Å, c=16.350(3)Å, α=90.00°, β=96.500(6)°, γ=90.00°, Z=4, V=744.2(2)Å 3 .

2. A method for preparing the nonlinear optical crystal of diguanidinyl phosphite as claimed in claim 1, characterized in that Growing crystals by evaporation, aqueous solution cooling, hydrothermal or solvothermal methods; The specific operation of growing the dihydroguanidino urea phosphite nonlinear optical crystal by the evaporation method is carried out in the following steps: a. Mix the compound containing [C2N4OH7] and the compound containing P uniformly in a molar ratio of [C2N4OH7]:P=1:0.8-1.2, add 20-100 ml of deionized water to mix, obtain a mixed solution, and then treat it with ultrasound to fully mix and dissolve it to obtain a clear solution; the compound containing [C2N4OH7] is C4H 12 N8O2·H2SO4、C4H 12 N8O2·H2CO3, C2N4OH6·HCl or C2N4OH6·HNO3; the P-containing compound is H3PO3, KH2PO3, Ca(H2PO3)2 or Ba(H2PO3)2; Or, in a molar ratio of [C2N4OH7]:P=1:0.8-1.2, the compound containing [C2N4H4] and the compound containing P are uniformly mixed, 20-100 ml of deionized water and 0-10 ml of protonic acid solution are added to mix, and then 0-10 ml of alkaline solution is added to obtain a mixed solution, and then ultrasonic treatment is performed to fully mix and dissolve it to obtain a clear solution; the compound containing [C2N4H4] is C2N4H4 (cyanoguanidine) organic matter; the compound containing P is H3PO3, KH2PO3, Ca (H2PO3) 2 or Ba (H2PO3) 2; the protonic acid solution is H2SO4 or HNO3; the alkaline solution is KOH; b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 20-85°C at a rate of 5-15°C / h, keep the temperature constant for 7-14 days to evaporate the solvent, and wait until the crystal growth is completed to obtain a guanidino urea phosphite nonlinear optical crystal; The aqueous solution cooling method for growing the diguanidino urea phosphite nonlinear optical crystal is specifically performed in the following steps: a. Mix the compound containing [C2N4OH7] and the compound containing P uniformly in a molar ratio of [C2N4OH7]:P=1:0.8-1.2, add 20-100 ml of deionized water to mix, obtain a mixed solution, and then treat it with ultrasound to fully mix and dissolve it to obtain a clear solution; the compound containing [C2N4OH7] is C4H 12 N8O2·H2SO4、C4H 12 N8O2·H2CO3, C2N4OH6·HCl or C2N4OH6·HNO3; the P-containing compound is H3PO3, KH2PO3, Ca(H2PO3)2 or Ba(H2PO3)2; Or, in a molar ratio of [C2N4OH7]:P=1:0.8-1.2, a compound containing [C2N4H4] and a compound containing P are uniformly mixed, 20-100 ml of deionized water and 0-10 ml of a protonic acid solution are added, and then 0-10 ml of an alkali solution is added to obtain a mixed solution, and then ultrasonic treatment is performed to fully mix and dissolve the mixed solution to obtain a clear solution; the compound containing [C2N4H4] is a C2N4H4 (cyanoguanidine) organic matter; the compound containing P is H3PO3, KH2PO3, Ca(H2PO3)2 or Ba(H2PO3)2; the protonic acid solution is H2SO4, HNO3, H3PO4 or HF; the alkali solution is KOH, NaOH, Ca(OH)2 or Ba(OH)2; b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 20-85°C at a rate of 5-15°C / h, keep the temperature constant for 3-7 days until the solution evaporates to saturation, and then cool it down to room temperature at a rate of 0.1-1°C / d to obtain a hydroxyphosphite aminoguanidine nonlinear optical crystal; The hydrothermal method for growing the diguanidinyl urea phosphite nonlinear optical crystal is specifically performed in the following steps: a. Mix the compound containing [C2N4OH7] and the compound containing P evenly in a molar ratio of [C2N4OH7]:P=1:0.8-1.2, add 5-10 ml of deionized water to mix, obtain a mixed solution, and then treat it with ultrasound to fully mix and dissolve it to obtain a clear solution; the compound containing [C2N4OH7] is C4H 12 N8O2·H2SO4、C4H 12 N8O2·H2CO3, C2N4OH6·HCl or C2N4OH6·HNO3; the P-containing compound is H3PO3, KH2PO3, Ca(H2PO3)2 or Ba(H2PO3)2; b. Transfer the mixed solution in step a into a polytetrafluoroethylene liner of a hydrothermal reactor with a volume of 23-100 ml, and tighten and seal the reactor; then heat it to 50-200°C at a rate of 10-20°C / h, keep it at a constant temperature for 2-5 days, and then cool it to room temperature at a rate of 1-2°C / h to obtain a dihydroguanidinyl urea nonlinear optical crystal; The solvothermal method for growing the dihydroguanidino urea phosphite nonlinear optical crystal is specifically performed in the following steps: a. Mix the compound containing [C2N4OH7] and the compound containing P uniformly at a molar ratio of [C2N4OH7]:P=1:0.8-1.2, add 20-100 ml of a mixed solution of deionized water and an organic solvent to obtain a mixed solution, and then treat it with ultrasound to fully mix and dissolve it to obtain a clear solution; the compound containing [C2N4OH7] is C4H 12 N8O2·H2SO4、C4H 12 N8O2·H2CO3, C2N4OH6·HCl or C2N4OH6·HNO3; the P-containing compound is H3PO3, KH2PO3, Ca(H2PO3)2 or Ba(H2PO3)2; b. Place the clarified solution in step a in a resistance furnace, raise the temperature to 20-85°C at a rate of 5-15°C / h, and keep it at a constant temperature for 7-14 days to evaporate the solvent. When the crystal growth is completed, a guanidino urea phosphite nonlinear optical crystal is obtained.

3. Use of the guanidino urea phosphite nonlinear optical crystal as claimed in claim 1 in preparing harmonic light output of 1064nm fundamental frequency light output by Nd:YAG laser for double, triple, quadruple and quintuple frequency multiplication.

4. Use of the guanidino urea phosphite nonlinear optical crystal as claimed in claim 1 in the preparation of ultraviolet frequency-doubled light output at or below 266 nm.

5. Use of the guanidinyl urea phosphite nonlinear optical crystal as claimed in claim 1 in the preparation of a frequency doubling generator, an up or down frequency converter or an optical parametric oscillator.

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