Compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal and preparation method and application thereof

Abstract

The present invention proposes a compound monohydrate monoboric acid dihydroxy decaborate dilead nonlinear optical crystal and its preparation method and application, belonging to the field of inorganic chemistry technology. The chemical formula of the crystal is Pb2B 10 O 16 (OH)2·B(OH)3·H2O, with a molecular weight of 892.35, belongs to the monoclinic crystal system, P21, and is grown in a closed system using a hydrothermal method or in an open system using a room temperature solution method. During the preparation process, the crystals grow easily and become transparent and unwrapped, with the advantages of fast growth rate, low cost, and easy acquisition of large-sized crystals. The obtained crystals have the advantages of light transmission band reaching the deep ultraviolet region, stable physical and chemical properties, non-deliquescent, easy processing and storage, and can be further used to prepare frequency doubling generators, up or down frequency converters, and optical parametric oscillators.

Description

Technical Field

[0001] The invention belongs to the technical field of inorganic chemistry, and in particular relates to a compound monohydrate monoboric acid dihydroxy dilead decaborate nonlinear optical crystal, a preparation method and an application thereof. Background Art

[0002] Borates have been a hot topic in the study of nonlinear crystal materials due to their excellent properties and rich structures. 2 and sp 3 Orbital hybridization can form [BO2] rods, [BO3] planar triangles and [BO4] tetrahedrons with O atoms. Borate NLO crystals containing π-conjugated [BO3] groups have moderate NLO coefficients, moderate birefringence, wide transmittance range and high laser damage threshold, such as β-BaB2O4·(β-BBO), LiB3O5·(LBO), CsB3O5·(CBO), CsLiB6O 10 (CLBO) has long been a research hotspot. By introducing hydroxyl groups, the three-dimensional structure of the BO group in borate can be regulated to construct a two-dimensional layered structure. Many hydroxyborates with excellent properties have been reported, such as AEB8O 15 H4(AE=Ca,Sr), Ba2[B6O9(OH)4], Zn2(BO3)(OH), CsB7O 10 (OH)2, Mg(H2O)6B4O5(OH)4(H2O)3, Ca2[B5O8(OH)]2[B(OH)3]·(OH)·4H2O and Ba2[B6O9(OH)2][B3O3(OH)4]·(OH)·4H2O.

[0003] In recent years, however, the development of new nonlinear optical crystals has focused not only on their optical and mechanical properties but also on their preparation characteristics. The goal is to make these new crystal materials easier to prepare, enabling the production of large, high-quality, and inexpensive nonlinear optical crystals. To this end, the present invention proposes a novel compound, dilead monohydrate monoborate dihydroxydecaborate, as well as a preparation method and application. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention proposes a novel compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal and its preparation method and application.

[0005] To achieve the above objectives, the present invention provides the following technical solutions:

[0006] The present invention proposes a compound monohydrate monoboric acid dihydroxy decaborate dilead nonlinear optical crystal, the chemical formula of the crystal is Pb2B 10 O16 (OH)2·B(OH)3·H2O, molecular weight is 892.35, belongs to monoclinic system, P21, unit cell parameters are β=119.0742(11)°,α=γ=90°,the unit cell volume is

[0007] The prior art relates to the preparation method and use of large-sized calcium ammonium borate octahydrate nonlinear optical crystals (patent application number CN201010606913.X), compound sodium borate monohydrate nonlinear optical crystals and their preparation method and use (patent application number CN201110339261.2), compound monohydroxy calcium pentaborate monohydrate nonlinear optical crystals and their preparation method and use (patent application number CN201410245947.9), and barium tetrahydroxyborate nonlinear optical crystals and their preparation method and use (patent application number CN201110365019.2). Compared with the above-mentioned nonlinear optical crystals, the compound monohydrate monoboric acid dihydroxy lead decaborate nonlinear optical crystals of the present invention have a unique two-dimensional anion framework. 2 [B5O8(OH)] ∞ Layer, this layer is parallel to the ac plane, and the two adjacent layers are arranged in opposite directions and back to back, and the crystal water and [B(OH)3] groups are filled in the two opposite layers. 2 [B5O8(OH)] ∞ Between the layers. Pb atoms fill 2 [B5O8(OH)] ∞ Within the 18-membered ring within the layer, the bonding forces of the layer structure constructed by the BOH group are different, resulting in completely different structures and growth habits.

[0008] The present invention also provides a method for preparing the compound monohydrate monoboric acid dilead dihydroxydecaborate nonlinear optical crystal, which is grown in a closed system by a hydrothermal method or in an open system by a room temperature solution method.

[0009] The hydrothermal method is to mix the lead-containing compound and the boron-containing compound and conduct a closed hydrothermal reaction in a hydrothermal kettle to prepare the product;

[0010] The room temperature solution method is to dissolve a lead-containing compound and a boron-containing compound in water to obtain a mixed solution, let it stand at room temperature to obtain a seed crystal, and suspend the seed crystal in the mixed solution with a fine platinum wire and let it stand at room temperature to grow.

[0011] Furthermore, the lead-containing compound is one or more of PbF2, PbO, PbCO3, Pb(NO3)2 or PbSO4; and the boron-containing compound is H3BO3 or B2O3.

[0012] Furthermore, the molar ratio of the lead-containing compound to the boron-containing compound is (2-4):11.

[0013] Furthermore, in the hydrothermal method, the hydrothermal reaction is heated to 150-220°C at a rate of 10-60°C / h, maintained at a constant temperature for 24-120h, and then cooled to room temperature at a rate of 1-50°C / h.

[0014] Furthermore, in the room temperature solution method, the mixed solution is allowed to stand at room temperature for 5-20 days to obtain seed crystals.

[0015] Furthermore, in the room temperature solution method, the seed crystal is suspended in the mixed solution and allowed to grow at room temperature for 10-30 days.

[0016] More specifically, the nonlinear optical crystal of dilead monohydrate monoborate dihydroxydecaborate of the present invention is synthesized by a hydrothermal method, which specifically includes the following steps:

[0017] A lead-containing compound (PbF2, PbO, PbCO3, Pb(NO3)2 or PbSO4) and a boron-containing compound (H3BO3 or B2O3) are uniformly mixed in a molar ratio of (2-4):11, placed in a hydrothermal kettle, and water is added. The mixture is placed in a constant temperature oven, heated to 150-220°C at a rate of 10-60°C / h, kept at a constant temperature for 24-120h, and then cooled to room temperature at a rate of 1-50°C / h to prepare the monohydrate monoboric acid dihydroxydecaborate nonlinear optical crystal.

[0018] More specifically, the nonlinear optical crystal of the monohydrate monoboric acid dilead dihydroxydecaborate of the present invention is synthesized by a room temperature solution method, which specifically includes the following steps:

[0019] a. Mix a lead-containing compound (PbF2, PbO, PbCO3, Pb(NO3)2, or PbSO4) and a boron-containing compound (H3BO3 or B2O3) in a molar ratio of (2-4):11, place the mixture in a clean glass container, add 20-100 mL of deionized water, and then ultrasonicate to fully mix and dissolve the mixture. Filter the mixture with filter paper to obtain a mixed solution.

[0020] b. Place the mixed solution obtained in step a in a clean glass container, seal it with weighing paper, place it in a static environment without shaking, pollution, or air convection, poke several small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and let it stand at room temperature for 5-20 days;

[0021] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0022] d. Select the transparent and crack-free seed crystal in step d, suspend it in the mixed solution prepared in step a with a fine platinum wire, and let it stand and grow at room temperature for 10-30 days to obtain a nonlinear optical crystal of dilead monoborate dihydroxydecaborate monohydrate.

[0023] Compared to the prior art calcium monoborate dihydroxydecaborate nonlinear optical crystal and its preparation method (CN201310504973.4), strontium monoborate dihydroxydecaborate nonlinear optical crystal and its preparation method (CN201310504651.X), and barium monoborate dihydroxydecaborate nonlinear optical crystal (CN201310504643.5), the present invention's lead monoborate dihydroxydecaborate nonlinear optical crystal can be stably grown in an open system (room temperature solution method) or in a closed system (hydrothermal method). Furthermore, the hydrothermal method preparation process does not require the addition of a mineralizer (lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia water, or ethylenediamine), resulting in the absence of other impurity ions, facilitating the production of high-quality single crystals. The preparation method of the present invention has the advantages of rapid growth, low cost, and ease of obtaining large-sized crystals.

[0024] The present invention is a nonlinear optical crystal of monohydrate monoboric acid dihydroxy lead decaborate (Pb2B 10 O 16 (OH)2·B(OH)3·H2O) Depending on the lead-containing compound and the boron-containing compound, the reaction formula of the synthesis process is different, for example:

[0025] 2PbF2+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+4HF+11H2O; or

[0026] 4PbO+11B2O3+7H2O→2Pb2B 10 O 16 (OH)2·B(OH)3·H2O; or

[0027] 2PbCO3+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2CO2+2H2O; or,

[0028] 4Pb(NO3)2+11B2O3+7H2O→2Pb2B 10 O 16 (OH)2·B(OH)3·H2O+4NO2; or

[0029] 2PbSO4+11H3BO3→Pb2B 10 O 16(OH)2·B(OH)3·H2O+2SO2+11H2O.

[0030] The present invention also proposes the use of the compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal in the preparation of a frequency doubling generator, an up or down frequency converter and an optical parametric oscillator.

[0031] Furthermore, the compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal is used to output harmonic light of the 1064nm fundamental frequency light output by the Nd:AG laser by frequency doubling and quadrupling.

[0032] Furthermore, the compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal is used to generate deep ultraviolet frequency-doubled light below 200nm.

[0033] Compared with the prior art, the present invention has the following advantages and technical effects:

[0034] (1) The nonlinear optical crystal of lead monohydrate monoborate dihydroxydecaborate (Pb2B 10 O 16 (OH)2·B(OH)3·H2O) is centimeter-sized. By controlling the standing time or hydrothermal reaction time, corresponding large-sized nonlinear optical crystals can be obtained. During the preparation process, the crystals are easy to grow, transparent and without wrapping, and have the advantages of fast growth rate, low cost, and easy to obtain large-sized crystals.

[0035] (2) The nonlinear optical crystal of lead monohydrate monoborate dihydroxydecaborate (Pb2B 10 O 16 (OH)2·B(OH)3·H2O) 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. It has the advantages of a light transmission band reaching the deep ultraviolet region (cut-off edge is 204nm), stable physical and chemical properties (thermogravimetric analysis at 100℃), and easy processing and storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The accompanying drawings, which constitute part of the present invention, are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are provided to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0037] Figure 1 Pb2B prepared in Example 1 of the present invention 10 O 16 Powder XRD pattern of (OH)2·B(OH)3·H2O crystals;

[0038] Figure 2 Pb2B prepared in Example 1 of the present invention 10 O 16 Schematic diagram of the structure of (OH)2·B(OH)3·H2O crystal;

[0039] Figure 3 For Pb2B 10 O 16 The working principle diagram of the nonlinear optical device made of (OH)2·B(OH)3·H2O crystal; 1 is the laser, 2 is the infrared beam, 3 is the Pb2B 10 O 16 (OH)2·B(OH)3·H2O crystal, 4 is the outgoing beam, and 5 is the filter. DETAILED DESCRIPTION

[0040] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0041] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any intermediate value within a stated value or stated range and any other stated value or intermediate value within the stated range is also encompassed by the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0042] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0043] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be illustrative only.

[0044] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0045] The embodiment of the present invention provides a compound monohydrate monoboric acid dihydroxy decaborate dilead nonlinear optical crystal, the chemical formula of the crystal is Pb2B 10 O 16 (OH)2·B(OH)3·H2O, molecular weight is 892.35, belongs to monoclinic system, P21, unit cell parameters are β=119.0742(11)°,α=γ=90°,the unit cell volume is

[0046] Pb2B prepared in the embodiment of the present invention 10 O 16 The (OH)2·B(OH)3·H2O anion framework is a unique two-dimensional 2 [B5O8(OH)] ∞ Layer, this layer is parallel to the ac plane, and the two adjacent layers are arranged in opposite directions and back to back, and the crystal water and [B(OH)3] groups are filled in the two opposite layers. 2 [B5O8(OH)] ∞ Between the layers. Pb atoms fill 2 [B5O8(OH)] ∞ Within the 18-membered ring within the layer, the bonding forces of the layer structure constructed by the BOH group are different, resulting in completely different structures and growth habits.

[0047] In the embodiment of the present invention, the obtained Pb2B 10 O 16 The size of (OH)2·B(OH)3·H2O is (1.0-1.7)cm×(0.8-1.5)cm×(0.5-1.0)cm, for example: 1.5cm×1.5cm×1.0cm, 1.5cm×1.3cm×0.8cm, 1.3cm×1.0cm×1.0cm, 1.7cm×1.4cm×0.8cm, 1.0cm×0.8cm×0.5cm and 1.0cm×0.8cm×0.5cm.

[0048] The present invention also provides a method for preparing the compound monohydrate monoboric acid dilead dihydroxydecaborate nonlinear optical crystal, which is grown in a closed system by a hydrothermal method or in an open system by a room temperature solution method.

[0049] The hydrothermal method is to mix the lead-containing compound and the boron-containing compound and conduct a closed hydrothermal reaction in a hydrothermal kettle to prepare the product;

[0050] The room temperature solution method is to dissolve a lead-containing compound and a boron-containing compound in water to obtain a mixed solution, let it stand at room temperature to obtain a seed crystal, and suspend the seed crystal in the mixed solution with a fine platinum wire and let it stand at room temperature to grow.

[0051] In a preferred embodiment of the present invention, the lead-containing compound is one or more of PbF2, PbO, PbCO3, Pb(NO3)2 or PbSO4; and the boron-containing compound is H3BO3 or B2O3.

[0052] In a preferred embodiment of the present invention, the molar ratio of the lead-containing compound to the boron-containing compound is (2-4):11.

[0053] In a preferred embodiment of the present invention, the hydrothermal reaction in the hydrothermal method is heated to 150-220°C at a rate of 10-60°C / h, kept at this temperature for 24-120 hours, and then cooled to room temperature at a rate of 1-50°C / h.

[0054] In a preferred embodiment of the present invention, in the room temperature solution method, the mixed solution is allowed to stand at room temperature for 5-20 days to obtain the seed crystals.

[0055] In a preferred embodiment of the present invention, in the room temperature solution method, the seed crystals are suspended in the mixed solution and allowed to grow at room temperature for 10-30 days.

[0056] In a preferred embodiment of the present invention, in the room temperature solution method, a transparent, crack-free seed crystal is suspended in the mixed solution by a fine platinum wire.

[0057] The present invention is a nonlinear optical crystal of monohydrate monoboric acid dihydroxy lead decaborate (Pb2B 10 O 16 (OH)2·B(OH)3·H2O) Depending on the lead-containing compound and the boron-containing compound, the reaction formula of the synthesis process is different, for example:

[0058] 2PbF2+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+4HF+11H2O; or

[0059] 4PbO+11B2O3+7H2O→2Pb2B 10 O 16 (OH)2·B(OH)3·H2O; or

[0060] 2PbCO3+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2CO2+2H2O; or,

[0061] 4Pb(NO3)2+11B2O3+7H2O→2Pb2B 10 O 16(OH)2·B(OH)3·H2O+4NO2; or

[0062] 2PbSO4+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2SO2+11H2O.

[0063] In the embodiments of the present invention, "room temperature" refers to "25±2°C".

[0064] The technical solution of the present invention is further illustrated by the following examples.

[0065] Example 1

[0066] Preparation of Pb2B by hydrothermal method 10 O 16 (OH)2·B(OH)3·H2O crystals

[0067] The lead-containing compound (PbF2) and the boron-containing compound (H3BO3) were mixed in a molar ratio of 2:11, placed in a hydrothermal kettle, and water was added according to the raw material and water mass ratio of 1:5. The mixture was placed in a constant temperature oven, heated to 220°C at a rate of 50°C / h, kept at this temperature for 120 hours, and then cooled to room temperature at a rate of 10°C / h to prepare a Pb2B with a size of 1.5 cm×1.5 cm×1.0 cm. 10 O 16 (OH)2·B(OH)3·H2O crystal. The synthesis reaction is: 2PbF2+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+4HF+11H2O.

[0068] Pb2B prepared in Example 1 of the present invention 10 O 16 The powder XRD spectrum of (OH)2·B(OH)3·H2O crystals is shown in Figure 1 , see the structural diagram Figure 2 ,according to Figure 1 and Figure 2 It can be explained that Pb2B 10 O 16 (OH)2·B(OH)3·H2O has a layered boron oxide anion group structure, which is composed of the basic building block [B5O 10 Parallel ac planes formed by the shared apex oxygen atoms between (OH)] groups 2 [B5O8(OH)] ∞ layer, which is similar to Figure 1 The preferred orientation in the middle (020) direction is consistent.

[0069] Example 2

[0070] Preparation of Pb2B by hydrothermal method 10 O 16 (OH)2·B(OH)3·H2O crystals

[0071] The lead compound (PbO) and the boron compound (B2O3) were mixed in a molar ratio of 4:11, placed in a hydrothermal kettle, and water was added. The mixture was placed in a constant temperature oven, heated to 220°C at a rate of 40°C / h, kept at this temperature for 100 hours, and then cooled to room temperature at a rate of 15°C / h to prepare a Pb2B3 with a size of 1.5 cm × 1.3 cm × 0.8 cm. 10 O 16 (OH)2·B(OH)3·H2O crystal. The synthesis process reaction formula is: 4PbO+11B2O3+7H2O→2Pb2B 10 O 16 (OH)2·B(OH)3·H2O.

[0072] Example 3

[0073] Preparation of Pb2B by hydrothermal method 10 O 16 (OH)2·B(OH)3·H2O crystals

[0074] The lead-containing compound (PbCO3) and the boron-containing compound (H3BO3) were mixed in a molar ratio of 2:11, placed in a hydrothermal kettle, and water was added. The mixture was placed in a constant temperature oven and heated to 210°C at a rate of 40°C / h, kept at this temperature for 80 hours, and then cooled to room temperature at a rate of 13°C / h to prepare a Pb2B with a size of 1.3 cm×1.0 cm×1.0 cm. 10 O 16 (OH)2·B(OH)3·H2O crystal. The synthesis reaction is: 2PbCO3+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2CO2+2H2O.

[0075] Example 4

[0076] Preparation of Pb2B by hydrothermal method 10 O 16 (OH)2·B(OH)3·H2O crystals

[0077] The lead compound (Pb(NO3)2) and the boron compound (B2O3) were mixed in a molar ratio of 4:11, placed in a hydrothermal kettle, and water was added. The mixture was placed in a constant temperature oven, heated to 220°C at a rate of 10°C / h, kept at this temperature for 120 hours, and then cooled to room temperature at a rate of 1°C / h to prepare a Pb2B with a size of 1.7 cm×1.4 cm×0.8 cm. 10 O 16 (OH)2·B(OH)3·H2O crystal. The synthesis reaction is: 4Pb(NO3)2+11B2O3+7H2O→2Pb2B 10 O 16 (OH)2·B(OH)3·H2O+4NO2.

[0078] Example 5

[0079] Preparation of Pb2B by hydrothermal method 10 O 16 (OH)2·B(OH)3·H2O crystals

[0080] The lead-containing compound (PbSO4) and the boron-containing compound (H3BO3) were mixed in a molar ratio of 2:11, placed in a hydrothermal kettle, and water was added. The mixture was placed in a constant temperature oven, heated to 190°C at a rate of 60°C / h, kept at this temperature for 120 hours, and then cooled to room temperature at a rate of 20°C / h to prepare a Pb2B with a size of 1.0 cm×0.8 cm×0.5 cm. 10 O 16 (OH)2·B(OH)3·H2O crystal. The synthesis reaction is: 2PbSO4+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2SO2+11H2O.

[0081] Example 6

[0082] Preparation of Pb2B by room temperature solution method 10 O 16 (OH)2·B(OH)3·H2O crystals

[0083] a. Mix the lead-containing compound (Pb(NO3)2) and the boron-containing compound (H3BO3) in a molar ratio of 2:11, place them in a clean glass container, add 100 mL of deionized water, and then ultrasonicate to fully mix and dissolve them. Filter with filter paper to obtain a mixed solution;

[0084] b. Place the mixed solution obtained in step a in a clean glass container, seal it with weighing paper, and place it in a static environment without shaking, pollution, or air convection. Poke 20 small holes in the seal to adjust the evaporation rate of water in the aqueous solution to 0.05 ml / day, and let it stand at room temperature for 10 days;

[0085] c. Waiting for the solution in step b to grow crystal particles at the bottom of the container until the size of the crystal particles no longer changes significantly, thereby obtaining seed crystals;

[0086] d. Select the transparent and crack-free seed crystal from step c, suspend it in the mixed solution prepared in step a with a fine platinum wire, and let it grow at room temperature for 20 days to prepare a Pb2B with a size of 1.0 cm × 0.8 cm × 0.5 cm. 10 O 16 (OH)2·B(OH)3·H2O crystal. The synthesis reaction is: 2PbSO4+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2SO2+11H2O.

[0087] Example 7

[0088] The same as Example 1, except that the temperature was raised to 150°C at a rate of 60°C / h, kept constant at that temperature for 120 hours, and then cooled to room temperature at a rate of 50°C / h to prepare Pb2B with a size of 0.5 cm×0.3 cm×0.1 cm. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0089] Example 8

[0090] The same as Example 1, except that the temperature was raised to 220°C at a rate of 10°C / h, kept constant for 24 hours, and then cooled to room temperature at a rate of 1°C / h to prepare Pb2B with a size of 1.0 cm × 0.8 cm × 0.5 cm. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0091] Example 9

[0092] Same as Example 6, except that in step b, the mixture was allowed to stand at room temperature for 5 days to prepare Pb2B with a size of 0.3 cm × 0.2 cm × 0.05 cm. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0093] Example 10

[0094] Same as Example 6, except that in step b, the Pb2B was allowed to stand at room temperature for 20 days to prepare a Pb2B with a size of 1.0 cm × 0.7 cm × 0.4 cm. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0095] Example 11

[0096] Same as Example 6, except that in step d, the Pb2B was grown at room temperature for 10 days to obtain a Pb2B with a size of 0.6 cm × 0.4 cm × 0.2 cm. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0097] Example 12

[0098] Same as Example 6, except that in step d, the Pb2B was grown at room temperature for 30 days to obtain a Pb2B with a size of 1.2 cm × 0.9 cm × 0.5 cm. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0099] Application Example 1

[0100] Use Pb2B 10 O 16 The working principle diagram of the nonlinear optical device made of (OH)2·B(OH)3·H2O crystal is shown in Figure 3 , where 1 is a laser, 2 is an infrared beam, and 3 is Pb2B 10 O 16 (OH)2·B(OH)3·H2O crystal, 4 is the outgoing beam, and 5 is the filter.

[0101] The Pb2B prepared in Example 1 10 O 16 (OH)2·B(OH)3·H2O crystals are processed in matching directions, according to Figure 3 As shown, it is installed at position 3. At room temperature, a Q-switched Nd:YAG laser is used as a light source. The infrared beam 2 with a wavelength of 1064 nm emitted by the Q-switched Nd:YAG laser 1 is incident on the Pb2B prepared in Example 1. 10 O 16 (OH)2·B(OH)3·H2O crystal 3. The remaining Examples 2-12 were assembled and tested according to the above method.

[0102] The results show that the Pb2B of Examples 1-12 10 O 16(OH)2·B(OH)3·H2O crystals can generate green doubled frequency light (emitted beam 4) with a wavelength of 532nm, and the output intensity is about 2.1 times that of KDP (potassium dihydrogen phosphate crystal) under the same conditions. This is because the Pb2B in Examples 1-12 crystallized in the P21 space group 10 O 16 (OH)2·B(OH)3·H2O crystals have the same structure and therefore have the same optical properties.

[0103] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A nonlinear optical crystal of a compound monohydrate monoboric acid dilead dihydroxydecaborate, characterized in that: The chemical formula of this crystal is Pb2B 10 O 16 (OH)2·B(OH)3·H2O, molecular weight is 892.35, belongs to monoclinic system, P21, unit cell parameters are β=119.0742(11)°,α=γ=90°,the unit cell volume is 2. A method for preparing a nonlinear optical crystal of the compound monohydrate monoboric acid dilead dihydroxydecaborate according to claim 1, characterized in that: It is grown in a closed system by a hydrothermal method or in an open system by a room temperature solution method; The hydrothermal method is to mix the lead-containing compound and the boron-containing compound and conduct a closed hydrothermal reaction in a hydrothermal kettle to prepare the product; The room temperature solution method is to dissolve a lead-containing compound and a boron-containing compound in water to obtain a mixed solution, let it stand at room temperature to obtain a seed crystal, and then suspend the seed crystal in the mixed solution and let it stand at room temperature to grow.

3. The method for preparing the nonlinear optical crystal of the compound monohydrate monoboric acid dilead dihydroxydecaborate according to claim 2, characterized in that: The lead-containing compound is one or more of PbF2, PbO, PbCO3, Pb(NO3)2 or PbSO4; the boron-containing compound is H3BO3 or B2O3.

4. The method for preparing the nonlinear optical crystal of the compound monohydrate monoboric acid dilead dihydroxydecaborate according to claim 2, characterized in that: The molar ratio of the lead-containing compound to the boron-containing compound is (2-4):

11.

5. The method for preparing the nonlinear optical crystal of the compound monohydrate monoboric acid dilead dihydroxydecaborate according to claim 2, characterized in that: In the hydrothermal method, the hydrothermal reaction is heated to 150-220°C at a rate of 10-60°C / h, kept at the temperature for 24-120h, and then cooled to room temperature at a rate of 1-50°C / h.

6. The method for preparing the nonlinear optical crystal of the compound monohydrate monoboric acid dilead dihydroxydecaborate according to claim 2, characterized in that: In the room temperature solution method, the mixed solution is allowed to stand at room temperature for 5-20 days to obtain seed crystals.

7. The method for preparing the compound monohydrate monoboric acid dilead dihydroxydecaborate nonlinear optical crystal according to claim 2, characterized in that: In the room temperature solution method, the seed crystal is suspended in the mixed solution and allowed to grow at room temperature for 10-30 days.

8. Use of the compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal as claimed in claim 1 in the preparation of a frequency doubling generator, an up or down frequency converter and an optical parametric oscillator.

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