Compound monoboric acid monohydrate dihydroxy lead decaborate nonlinear optical crystal as well as preparation method and application thereof

Abstract

The invention provides a compound monoboric acid monohydrate dihydroxy lead decaborate nonlinear optical crystal as well as a preparation method and application thereof, and belongs to the technical field of inorganic chemistry. The chemical formula of the crystal is Pb2B10O16 (OH) 2. B (OH) 3. H2O, the molecular weight is 892.35, the crystal belongs to a monoclinic system and P21, the crystal is obtained by growing in a closed system by adopting a hydrothermal method or growing in an open system by adopting a room temperature solution method, the crystal is easy to grow up, transparent and unwrapped in the preparation process, and the crystal has the advantages that the growth speed is high, the cost is low, a large-size crystal is easy to obtain and the like. The obtained crystal has the advantages that the light transmission wave band reaches a deep ultraviolet region, physical and chemical properties are stable, deliquescence is not easy, processing and storage are easy, and the like, and can be further used for preparing a frequency doubling generator, an upper or lower frequency converter and an optical parametric oscillator.

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 and a preparation method and application thereof. Background Art

[0002] Borates have been a hot topic in the study of nonlinear crystalline 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 light transmission range and high laser damage threshold, such as β-BaB2O4·(β-BBO), LiB3O5·(LBO), CsB3O5·(CBO), CsLiB6O 10 (CLBO) has long been a hot topic of research. 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] However, in recent years, when developing new nonlinear optical crystals, people not only pay attention to the optical and mechanical properties of the crystals, but also pay more and more attention to the preparation characteristics of the crystals. It is hoped that the new crystal materials can be easily prepared, and low-cost large-size and high-quality nonlinear optical crystals can be obtained. For this reason, the present invention proposes a new compound monohydrate monoboric acid dihydroxy decaboric acid dilead nonlinear optical crystal and its 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 dihydroxy dilead decaborate nonlinear optical crystal, and a preparation method and application thereof.

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

[0006] The present invention provides a compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal, the chemical formula of which 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

[0008] The prior art relates to a preparation method and use of a large-sized calcium ammonium borate octahydrate nonlinear optical crystal (patent application number is CN201010606913.X), a compound sodium borate monohydrate nonlinear optical crystal and its preparation method and use (patent application number is CN201110339261.2), a compound calcium pentaborate monohydrate nonlinear optical crystal and its preparation method and use (patent application number is CN201410245947.9), and a barium tetrahydroxyborate nonlinear optical crystal and its preparation method and use (patent application number is CN201110365019.2). Compared with the above nonlinear optical crystals, the compound monoborate dihydroxy dilead decaborate nonlinear optical crystal of the present invention has 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 2 [B5O8(OH)] ∞ The Pb atoms fill the interlayer 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.

[0009] The present invention also provides a method for preparing the compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal, which is grown in a closed system by a hydrothermal method or grown in an open system by a room temperature solution method;

[0010] The hydrothermal method is to mix the lead-containing compound and the boron-containing compound and carry out a closed hydrothermal reaction in a hydrothermal kettle to prepare the compound;

[0011] 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.

[0012] 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.

[0013] Furthermore, the molar ratio of the lead-containing compound to the boron-containing compound is (2-4):11.

[0014] 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.

[0015] Furthermore, 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.

[0016] 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.

[0017] More specifically, the nonlinear optical crystal of dilead monohydrate monoboric acid dihydroxydecaborate of the present invention is synthesized by a hydrothermal method, which specifically includes the following steps:

[0018] 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, loaded into a hydrothermal kettle, and water is added, 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.

[0019] More specifically, the nonlinear optical crystal of dilead monoboric acid dihydroxydecaborate monohydrate of the present invention is synthesized by a room temperature solution method, which specifically includes the following steps:

[0020] 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, put them into a clean glass container, add 20-100 mL of deionized water, and then treat with ultrasonic wave to fully mix and dissolve them, and filter with filter paper to obtain a mixed solution;

[0021] 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, pierce a number of small holes in the seal to adjust the evaporation rate of water in the aqueous solution, and leave it at room temperature for 5-20 days;

[0022] 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;

[0023] 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 the nonlinear optical crystal of dilead monoboric acid dihydroxydecaborate monohydrate.

[0024] Compared with the prior art monohydrate monoboric acid dihydroxy calcium decaborate nonlinear optical crystal and its preparation method (CN201310504973.4), monohydrate monoboric acid dihydroxy strontium decaborate nonlinear optical crystal and its preparation method (CN201310504651.X), monohydrate monoboric acid dihydroxy barium decaborate nonlinear optical crystal (CN201310504643.5), the monohydrate monoboric acid dihydroxy lead decaborate nonlinear optical crystal of the present invention can be stably grown in an open system (room temperature solution method), and can also be grown and prepared in a closed system (hydrothermal method), and no mineralizer (lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia water or ammonia water or ethylenediamine) needs to be added during the hydrothermal preparation process, and the advantage is that no other impurity ions will be introduced, so that a high-quality single crystal can be obtained. The preparation method of the present invention has the advantages of fast growth rate, low cost, easy acquisition of large-sized crystals, etc.

[0025] The present invention discloses a nonlinear optical crystal of dilead monohydrate monoboric acid dihydroxydecaborate (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:

[0026] 2PbF2+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+4HF+11H2O; or,

[0027] 4PbO+11B2O3+7H2O→2Pb2B 10 O 16 (OH)2·B(OH)3·H2O; or,

[0028] 2PbCO3+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2CO2+2H2O; or,

[0029] 4Pb(NO3)2+11B2O3+7H2O→2Pb2B 10 O 16 (OH)2·B(OH)3·H2O+4NO2; or,

[0030] 2PbSO4+11H3BO3→Pb2B 10 O 16(OH)2·B(OH)3·H2O+2SO2+11H2O.

[0031] The 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.

[0032] 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 at the doubled and quadrupled frequencies.

[0033] Furthermore, the compound monohydrate monoboric acid dihydroxy dilead decaborate nonlinear optical crystal is used to generate deep ultraviolet doubled frequency light below 200nm.

[0034] Compared with the prior art, the present invention has the following advantages and technical effects:

[0035] (1) The nonlinear optical crystal of dilead monohydrate monoboric acid 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.

[0036] (2) The nonlinear optical crystal of dilead monohydrate monoboric acid 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 (thermal gravity 100℃), and easy processing and storage. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0038] Figure 1 The Pb2B prepared in Example 1 of the present invention 10 O 16 Powder XRD pattern of (OH)2·B(OH)3·H2O crystals;

[0039] Figure 2 The 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;

[0040] 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 light beam, and 5 is the filter. DETAILED DESCRIPTION

[0041] 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 should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0042] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0043] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation 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 a conflict with any incorporated document, the content of this specification shall prevail.

[0044] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0045] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0046] The embodiment of the present invention provides a compound monohydrate monoboric acid dihydroxy decaboric acid 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

[0048] 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 2 [B5O8(OH)] ∞ The Pb atoms fill the interlayer 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.

[0049] 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.

[0050] The embodiment of the present invention also provides a method for preparing the compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal, which is grown in a closed system by a hydrothermal method or grown in an open system by a room temperature solution method;

[0051] The hydrothermal method is to mix the lead-containing compound and the boron-containing compound and carry out a closed hydrothermal reaction in a hydrothermal kettle to prepare the compound;

[0052] 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.

[0053] 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; the boron-containing compound is H3BO3 or B2O3.

[0054] 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.

[0055] In a preferred embodiment of the present invention, the hydrothermal reaction in the hydrothermal method is heated to 150-220°C at 10-60°C / h, kept at a constant temperature for 24-120 hours, and then cooled to room temperature at a rate of 1-50°C / h.

[0056] 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.

[0057] In a preferred embodiment of the present invention, 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.

[0058] 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.

[0059] The present invention discloses a nonlinear optical crystal of dilead monohydrate monoboric acid dihydroxydecaborate (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:

[0060] 2PbF2+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+4HF+11H2O; or,

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

[0062] 2PbCO3+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2CO2+2H2O; or,

[0063] 4Pb(NO3)2+11B2O3+7H2O→2Pb2B 10 O 16(OH)2·B(OH)3·H2O+4NO2; or,

[0064] 2PbSO4+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2SO2+11H2O.

[0065] In the embodiments of the present invention, "room temperature" refers to "25±2°C".

[0066] The technical solution of the present invention is further illustrated by the following embodiments.

[0067] Example 1

[0068] Preparation of Pb2B by hydrothermal method 10 O 16 (OH)2·B(OH)3·H2O crystal

[0069] The lead-containing compound (PbF2) and the boron-containing compound (H3BO3) were mixed uniformly at a molar ratio of 2:11, loaded into a hydrothermal kettle, and water was added at a raw material to water mass ratio of 1:5, placed in a constant temperature oven, heated to 220°C at 50°C / h, kept at a constant 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 1.5cm×1.5cm×1.0cm 10 O 16 (OH)2·B(OH)3·H2O crystal. The reaction formula of the synthesis process is: 2PbF2+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+4HF+11H2O.

[0070] 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 , the structural diagram is shown in 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 The parallel ac planes formed by the (OH)] groups connected by shared vertex oxygen atoms 2 [B5O8(OH)] ∞ layer, which is similar to Figure 1 The preferred orientation in the middle (020) direction is consistent.

[0071] Example 2

[0072] Preparation of Pb2B by hydrothermal method 10 O 16 (OH)2·B(OH)3·H2O crystal

[0073] 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 a constant 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.

[0074] Example 3

[0075] Preparation of Pb2B by hydrothermal method 10 O 16 (OH)2·B(OH)3·H2O crystal

[0076] The lead-containing compound (PbCO3) and the boron-containing compound (H3BO3) were mixed uniformly 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 210°C at a rate of 40°C / h, kept at a constant 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 reaction formula of the synthesis process is: 2PbCO3+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2CO2+2H2O.

[0077] Example 4

[0078] Preparation of Pb2B by hydrothermal method 10 O 16 (OH)2·B(OH)3·H2O crystal

[0079] The lead compound (Pb(NO3)2) and the boron compound (B2O3) were mixed in a molar ratio of 4:11, put into a hydrothermal kettle, added with water, placed in a constant temperature oven, heated to 220°C at a rate of 10°C / h, kept at a constant temperature for 120 hours, and then cooled to room temperature at a rate of 1°C / h to prepare a Pb2B 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.

[0080] Example 5

[0081] Preparation of Pb2B by hydrothermal method 10 O 16 (OH)2·B(OH)3·H2O crystal

[0082] The lead-containing compound (PbSO4) and the boron-containing compound (H3BO3) were mixed uniformly 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 the constant 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 reaction formula of the synthesis process is: 2PbSO4+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2SO2+11H2O.

[0083] Example 6

[0084] Preparation of Pb2B by room temperature solution method 10 O 16 (OH)2·B(OH)3·H2O crystal

[0085] a. Mix the lead-containing compound (Pb(NO3)2) and the boron-containing compound (H3BO3) in a molar ratio of 2:11, put them into a clean glass container, add 100 mL of deionized water, and then treat with ultrasonic wave to fully mix and dissolve them, and filter with filter paper to obtain a mixed solution;

[0086] 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, pierce the seal with 20 small holes to adjust the evaporation rate of water in the aqueous solution to 0.05 ml / day, and leave it at room temperature for 10 days;

[0087] 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;

[0088] d. Select the transparent and crack-free seed crystal in step c, suspend it in the mixed solution prepared in step a with a fine platinum wire, and let it stand for 20 days at room temperature 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 reaction formula of the synthesis process is: 2PbSO4+11H3BO3→Pb2B 10 O 16 (OH)2·B(OH)3·H2O+2SO2+11H2O.

[0089] Example 7

[0090] The same as Example 1, except that the temperature was raised to 150°C at a rate of 60°C / h, kept constant for 120 hours, and then cooled to room temperature at a rate of 50°C / h to prepare a Pb2B with a size of 0.5 cm×0.3 cm×0.1 cm 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0091] Example 8

[0092] 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 a Pb2B having a size of 1.0 cm×0.8 cm×0.5 cm. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0093] Example 9

[0094] Same as Example 6, except that in step b, the mixture was allowed to stand at room temperature for 5 days to prepare a Pb2B having a size of 0.3 cm×0.2 cm×0.05 cm. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0095] Example 10

[0096] Same as Example 6, except that in step b, the mixture was allowed to stand at room temperature for 20 days to prepare a Pb2B having a size of 1.0 cm×0.7 cm×0.4 cm. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0097] Embodiment 11

[0098] Same as Example 6, except that in step d, the Pb2B with a size of 0.6 cm × 0.4 cm × 0.2 cm was prepared by standing at room temperature for 10 days. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0099] Example 12

[0100] Same as Example 6, except that in step d, the Pb2B with a size of 1.2 cm × 0.9 cm × 0.5 cm was prepared by standing at room temperature for 30 days. 10 O 16 (OH)2·B(OH)3·H2O crystals.

[0101] Application Example 1

[0102] With 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 light beam, and 5 is the filter.

[0103] The Pb2B prepared in Example 1 10 O 16 (OH)2·B(OH)3·H2O crystals are processed in matching directions. Figure 3 As shown, the Q-switched Nd:YAG laser 1 is installed at the position of serial number 3. At room temperature, the Q-switched Nd:YAG laser 1 is used as the light source. The infrared beam 2 with a wavelength of 1064 nm emitted by the Q-switched Nd:YAG laser 1 is respectively 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.

[0104] The results show that the Pb2B of Examples 1-12 10 O 16(OH)2·B(OH)3·H2O crystals can generate green double frequency light (emission 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 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.

[0105] The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. Compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal, 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 the compound monohydrate monoboric acid dilead dihydroxydecaborate nonlinear optical crystal 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 carry out a closed hydrothermal reaction in a hydrothermal kettle to prepare the compound; The room temperature solution method is to dissolve the lead-containing compound and the 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 and let it stand at room temperature to grow.

3. The method for preparing the compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal 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 compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal 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 compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal according to claim 2, characterized in that: In the hydrothermal method, the hydrothermal reaction is heated to 150-220°C at 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.

6. The method for preparing the compound monohydrate monoboric acid dihydroxydecaborate dilead nonlinear optical crystal 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 dihydroxydecaborate dilead 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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