WO2020024179A1 - 碱金属氰尿酸一氢盐化合物、其晶体及其制备方法与应用 - Google Patents

碱金属氰尿酸一氢盐化合物、其晶体及其制备方法与应用 Download PDF

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WO2020024179A1
WO2020024179A1 PCT/CN2018/098122 CN2018098122W WO2020024179A1 WO 2020024179 A1 WO2020024179 A1 WO 2020024179A1 CN 2018098122 W CN2018098122 W CN 2018098122W WO 2020024179 A1 WO2020024179 A1 WO 2020024179A1
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crystal
compound
monohydrogen
cyanurate
lithium
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PCT/CN2018/098122
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French (fr)
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叶宁
林栋鸿
罗敏
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中国科学院福建物质结构研究所
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Priority to JP2021503086A priority Critical patent/JP7212757B2/ja
Priority to US17/263,658 priority patent/US20210309673A1/en
Priority to PCT/CN2018/098122 priority patent/WO2020024179A1/zh
Publication of WO2020024179A1 publication Critical patent/WO2020024179A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/02—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/32—Cyanuric acid; Isocyanuric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/04—Sodium compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/353—Frequency conversion, i.e. wherein a light beam is generated with frequency components different from those of the incident light beams
    • G02F1/354—Third or higher harmonic generation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/3551—Crystals
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/37—Non-linear optics for second-harmonic generation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/39—Non-linear optics for parametric generation or amplification of light, infrared or ultraviolet waves
    • G02F1/392—Parametric amplification

Definitions

  • the invention belongs to the technical field of optoelectronic functional materials, and particularly relates to an alkali metal cyanuric acid monohydrogen salt compound, a crystal thereof, and a preparation method and application thereof.
  • the nonlinear optical effect of a crystal refers to an effect: when a laser beam with a certain polarization direction passes through a nonlinear optical crystal (such as a borate nonlinear optical crystal) in a certain incident direction, the frequency of the beam will Changed.
  • a nonlinear optical crystal such as a borate nonlinear optical crystal
  • nonlinear optical crystals Crystals with non-linear optical effects are called nonlinear optical crystals.
  • the use of nonlinear optical crystals for laser frequency conversion broadens the range of laser wavelengths and makes lasers more widely used.
  • Especially borate nonlinear optical crystals such as BaB 2 O 4 (BBO), LiB 3 O 5 (LBO), KBe 2 BO 3 F 2 (KBBF), Sr 2 Be 2 B 2 O 7 (SBBO), Ba 2 Be 2 B 2 O 7 (TBO), K 2 Al 2 B 2 O 7 (KABO), BaAl 2 B 2 O 7 (BABO) and other crystals have attracted much attention for their excellent optical properties.
  • the basic structural element of BBO crystal is (B 3 O 6 ) 3- plane group.
  • the basic structural element of KBBF is (BO 3 ) 3- plane group.
  • ⁇ n 0.07
  • the best deep ultraviolet nonlinear optical crystal to date because KBBF is a layered structure crystal, the layers are connected by electrostatic attraction instead of being connected through valence bonds.
  • the layered habit is serious, the growth rate in the z direction is very slow, and the single crystal grown grows out of layers. Obviously, crystals are not easy to grow.
  • the basic structural element of SBBO is also a (BO 3 ) 3- plane group, but it replaces fluorine ions with oxygen, so that the layers are connected to each other through oxygen bridges in order to improve the layered habit of KBBF.
  • the structure remains essentially the same.
  • the structural conditions of the (BO 3 ) 3- group are basically unchanged, and the cationic Sr 2+ and Be atoms are replaced.
  • a series of non-linear optical crystals such as TBO, KABO, and BABO have been developed. They are collectively called SBBO. Family crystals. They overcome the layered habit of KBBF single crystal growth, but these crystals have not been able to replace KBBF single crystals so far, because the structural integrity of TBO crystals is not good, and their macroscopic properties show very poor optical uniformity. It has been used in practical devices; KABO and BABO crystals have good structural integrity and good optical uniformity, but because Al replaces Be, their absorption edges are red-shifted to about 180 nm, which is difficult to use for deep ultraviolet resonance. Wave output.
  • the basic structural element of LBO is to change a B atom in the (B 3 O 6 ) 3- group from a tri-coordination to a tetra-coordination to form a (B 3 O 7 ) 5- group. It has a large frequency doubling coefficient, and the ultraviolet absorption edge is about 160nm, but because (B 3 O 7 ) 5 -groups in the actual crystal are connected to each other, a spiral chain at 45 ° to the z-axis is formed in the space.
  • the present invention provides an alkali metal cyanuric acid monohydrogen salt compound, the chemical formula of which is AM (HC 3 N 3 O 3 ) nH 2 O, wherein A and M are the same or different and are independent of each other Ground is selected from alkali metals, such as Li, Na, K, Rb, Cs, Fr; n is selected from an integer of 0 or more.
  • n is selected from an integer of 0-10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, preferably 2.
  • the compound may be selected from the group consisting of lithium potassium monohydrogen cyanurate dihydrate (chemical formula: KLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O; abbreviated KLHCY), lithium monohydrogen cyanurate dihydrate (Chemical formula: RbLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O; RLHCY for short), sodium monohydrogen cyanurate dihydrate (chemical formula: RbNa (HC 3 N 3 O 3 ) ⁇ 2H 2 O; RNHCY for short).
  • the compound may be in the form of a non-linear optical crystal.
  • the invention also provides a non-linear optical crystal of potassium lithium monohydrogen cyanurate dihydrate, whose chemical formula is KLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O.
  • the lithium potassium monohydrogen cyanurate dihydrate nonlinear optical crystal has an X-ray powder diffraction pattern substantially as shown in FIG. 3.
  • the invention also provides a non-linear optical crystal of lithium rhenium monohydrogen cyanurate dihydrate, whose chemical formula is RbLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O.
  • the lithium rhenium dihydrogen cyanurate dihydrogen nonlinear optical crystal has an X-ray powder diffraction pattern substantially as shown in FIG. 4.
  • the invention also provides a nonlinear optical crystal of sodium monohydrogen cyanurate dihydrate, the chemical formula of which is RbNa (HC 3 N 3 O 3 ) 2H 2 O.
  • the sodium monohydrogen cyanurate dihydrate non-linear optical crystal has an X-ray powder diffraction pattern substantially as shown in FIG. 5.
  • the invention also provides a method for preparing the above-mentioned alkali metal cyanuric acid monohydrogen compound, which comprises reacting AOH ⁇ xH 2 O, MOH ⁇ yH 2 O and H 3 C 3 N 3 O 3 to obtain alkali metal cyanuric acid monohydrogen A salt compound; wherein A and M have the definitions described above; x and y are the same or different and are independently selected from integers of 0 or more.
  • x and y are the same or different and are independently selected from integers of 0-10, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and preferably 0, 1.
  • the molar ratio of the AOH ⁇ xH 2 O, MOH ⁇ yH 2 O and H 3 C 3 N 3 O 3 may be (0.5 ⁇ 2.5) :( 0.5 ⁇ 2.5): 1, preferably (0.8 ⁇ 1.2) :( 0.8 ⁇ 1.2): 1, such as 1: 1: 1.
  • the reaction may be performed in a solvent, and the solvent may be selected from an organic solvent or an inorganic solvent, preferably an inorganic solvent such as water;
  • the ratio of the total mass of the raw materials to the solvent may be 5 to 50 g of raw materials / 100 ml of solvent, and preferably 10 to 30 g of raw materials / 100 ml of solvent;
  • the reaction temperature may be 50 to 110 ° C, preferably 60 to 100 ° C, such as 80 ° C;
  • the reaction solution may be cooled at a constant cooling rate; after the temperature is reduced, the solvent is washed to obtain an alkali metal cyanuric acid monohydrogen compound;
  • the cooling rate is 1 to 10 ° C / hour, preferably 1 to 5 ° C / hour, such as 1 ° C / hour, 5 ° C / hour;
  • the temperature of the reaction solution is lowered to 0 to 40 ° C, preferably 10 to 40 ° C, such as 10 ° C, 40 ° C;
  • the solvent used for washing is water, acetone, or a mixture thereof, and the solvent can be used for washing multiple times; preferably, the solvent used for washing is acetone.
  • a crystal is prepared by using the above method, and the volume of the crystal is greater than 2.0 mm 3 .
  • the invention also provides the use of the above-mentioned alkali metal cyanuric acid monohydrogen compound (such as a crystal), which can be used for frequency conversion of laser output of laser, harmonic generator in ultraviolet region, optical parameter and amplifier device, and optical waveguide device;
  • alkali metal cyanuric acid monohydrogen compound such as a crystal
  • the compound can generate a harmonic light output of 2 times or 3 times or 4 times or 5 times or 6 times of the laser beam having a wavelength of 1.064 ⁇ m;
  • the compound can be used for optical parameters and amplifying devices in the infrared to ultraviolet region.
  • the present invention provides chemical formulas AM (HC 3 N 3 O 3 ) ⁇ nH 2 O (specifically, such as KLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O, RbLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O, RbNa (HC 3 N 3 O 3 ) ⁇ 2H 2 O) alkali metal cyanuric acid monohydrogen cyanide compound and its non-linear optical crystal, the non-linear optical crystal has strong phase matching ability (measured by powder doubling test method) , Its powder frequency doubling effect is about 2-3 times of KH 2 PO 4 (KDP)); its UV absorption edge is shorter than 250nm.
  • AM HC 3 N 3 O 3
  • nH 2 O specifically, such as KLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O, RbLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O, RbNa (HC 3 N 3 O 3 ) ⁇ 2H 2 O
  • the nonlinear optical crystal has a single crystal structure, is colorless and transparent, and does not deliquesce in the air.
  • AM (HC 3 N 3 O 3 ) ⁇ nH 2 O (specifically, such as KLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O, RbLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O, RbNa ( HC 3 N 3 O 3 ) ⁇ 2H 2 O) will be widely used in various non-linear optical fields, and will open up non-linear optical applications in the ultraviolet band.
  • Figure 1 is a typical schematic diagram of nonlinear optical effects when KLHCY, RLHCY, and RNHCY crystals are used as frequency-doubling crystals, where 1 is a laser, 2 is an incident laser beam, 3 is a single crystal that has undergone crystal post-processing and optical processing, and 4 is the generated Of the outgoing laser beam, 5 is a filter.
  • FIG. 2 is a schematic structural diagram of KLHCY, RLHCY, and RNHCY crystals (KLHCY, RLHCY, and RNHCY are isomorphic compounds).
  • FIG. 3 is an X-ray diffraction pattern of a KLHCY single crystal after being ground into a powder.
  • FIG. 4 is an X-ray diffraction pattern of the RLHCY single crystal after being ground into a powder.
  • FIG. 5 is an X-ray diffraction pattern of the RNHCY single crystal after being ground into a powder.
  • the present invention provides a compound having a completely new structure and a crystal thereof, and its structural formula is AM (HC 3 N 3 O 3 ) ⁇ nH 2 O (specifically, such as KLHCY, RLHCY, RNHCY), among which monohydrogen cyanurate Roots provide excellent aqueous growth and non-linear properties for crystal growth.
  • AM HC 3 N 3 O 3
  • nH 2 O specifically, such as KLHCY, RLHCY, RNHCY
  • the specific operation steps are as follows: After weighing the above raw materials according to the above dosage, put them into a 100ml beaker, put a magnet, put the beaker on a magnetic heating stirrer, and heat the beaker to 80 ° C while stirring, and then raise the beaker The cooling rate per hour is reduced to 40 ° C. After cooling, the sample was washed with acetone to obtain a KLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O single crystal having a size of 5 ⁇ 1 ⁇ 1 mm.
  • the specific operation steps are as follows: After weighing the above raw materials according to the above dosage, put them into a 100ml beaker, put a magnet, put the beaker on a magnetic heating stirrer, and heat the beaker to 80 ° C while stirring, and then raise the beaker The cooling rate per hour is reduced to 40 ° C. After cooling, the sample was washed with acetone to obtain RbLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O single crystal with a size of 1 ⁇ 1 ⁇ 5 mm.
  • the specific operation steps are as follows: After weighing the above raw materials according to the above dosage, put them into a 100ml beaker, put a magnet, put the beaker on a magnetic heating stirrer, and heat the beaker to 80 ° C while stirring, and then raise the beaker The cooling rate of °C per hour is reduced to 10 °C. After cooling, the sample was washed with acetone to obtain RbNa (HC 3 N 3 O 3 ) ⁇ 2H 2 O single crystal with a size of 1 ⁇ 5 ⁇ 1 mm.
  • the specific operation steps are as follows: After weighing the above raw materials according to the above dosage, put them into a 100ml beaker, put a magnet, put the beaker on a magnetic heating stirrer, heat the beaker while stirring to 80 ° C, and then raise the beaker by 1 The cooling rate per hour is reduced to 40 ° C. After cooling, the sample was washed with acetone to obtain a KLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O single crystal with a size of 5 ⁇ 2 ⁇ 2 mm.
  • the specific operation steps are as follows: After weighing the above raw materials according to the above dosage, put them into a 100ml beaker, put a magnet, put the beaker on a magnetic heating stirrer, heat the beaker while stirring to 80 ° C, and then increase The cooling rate per hour is reduced to 40 ° C. After cooling, the sample was washed with acetone to obtain RbLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O single crystal with a size of 2 ⁇ 2 ⁇ 5 mm.
  • the specific operation steps are as follows: After weighing the above raw materials according to the above dosage, put them into a 100ml beaker, put a magnet, put the beaker on a magnetic heating stirrer, heat the beaker while stirring to 80 ° C, and then raise the beaker by 1 The cooling rate of °C per hour is reduced to 10 °C. After cooling, the sample was washed with acetone to obtain RbNa (HC 3 N 3 O 3 ) ⁇ 2H 2 O single crystal with a size of 2 ⁇ 5 ⁇ 2 mm.
  • the KLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O, RbLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O, and RbNa (HC 3 N 3 O 3 ) ⁇ 2H 2 O crystals obtained in Example 2 were processed and processed. After cutting, aligning and polishing, it is placed at 3 in the device shown in Figure 1.
  • a Q-switched Nd: YAG laser is used as the input light source.
  • the incident wavelength is 1064nm. Obvious green frequency output at 532nm is observed.
  • the output intensity is about 2-3 times the KDP of the same condition.
  • the output intensity of KLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O crystal is about three times that of the same condition KDP, and the output intensity of RbLi (HC 3 N 3 O 3 ) ⁇ 2H 2 O crystal is about the same condition.
  • the output intensity of RbNa (HC 3 N 3 O 3 ) ⁇ 2H 2 O crystal is twice that of KDP, which is about twice that of KDP under the same conditions.

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Abstract

本发明属于光电子功能材料技术领域，具体涉及碱金属氰尿酸一氢盐化合物、其晶体及其制备方法与应用。本发明提供了化学式为AM(HC 3N 3O 3)·nH 2O(具体如KLi(HC 3N 3O 3)·2H 2O、RbLi(HC 3N 3O 3)·2H 2O、RbNa(HC 3N 3O 3)·2H 2O)的碱金属氰尿酸一氢盐化合物及其非线性光学晶体，该非线性光学晶体具有极强的相位匹配能力(使用粉末倍频测试方法测量，其粉末倍频效应约为KH 2PO 4(KDP)的2-3倍)；其紫外吸收边短于250nm。另外，该非线性光学晶体能够实现Nd:YAG(λ＝1.064μm)的2倍频、3倍频、4倍频的谐波发生器。并且，该非线性光学晶体为单晶结构，无色透明，在空气中不潮解。所以可以预见，AM(HC 3N 3O 3)·nH 2O(具体如KLi(HC 3N 3O 3)·2H 2O、RbLi(HC 3N 3O 3)·2H 2O、RbNa(HC 3N 3O 3)·2H 2O)将在各种非线性光学领域中获得广泛应用，并将开拓紫外波段的非线性光学应用。

Description

碱金属氰尿酸一氢盐化合物、其晶体及其制备方法与应用 技术领域
本发明属于光电子功能材料技术领域，具体涉及碱金属氰尿酸一氢盐化合物、其晶体及其制备方法与应用。
背景技术
晶体的非线性光学效应是指这样一种效应：当一束具有某种偏振方向的激光按一定入射方向通过一块非线性光学晶体(如硼酸盐类非线性光学晶体)时，该光束的频率将发生变化。
具有非线型光学效应的晶体称为非线性光学晶体。利用非线性光学晶体进行激光频率转换，拓宽激光波长的范围，使激光的应用更加广泛。尤其是硼酸盐类非线性光学晶体如BaB 2O 4(BBO)、LiB 3O 5(LBO)、KBe 2BO 3F 2(KBBF)、Sr 2Be 2B 2O 7(SBBO)、Ba 2Be 2B 2O 7(TBO)、K 2Al 2B 2O 7(KABO)、BaAl 2B 2O 7(BABO)等晶体以其优异的光学性质而倍受关注。在光学照相、光刻蚀、精密仪器加工等领域的发展越来越需要紫外和深紫外激光相干光源，即需要性能优异的紫外和深紫外非线性光学晶体。
BBO晶体的基本结构基元是(B 3O 6) 3-平面基团，这种基团具有大的共轭π键，使得BBO的紫外吸收边在189nm左右，限制了晶体在紫外区的应用；且大的共轭π键也会导致较大的双折射率(Δn＝0.12)，从而限制了它的谐波转换效率及谐波光的质量。
KBBF的基本结构基元是(BO 3) 3-平面基团，此晶体的紫外吸收边在155nm左右，具有适中的双折射率(Δn＝0.07)，可以实现很宽的相位匹配范围，是目前为止最优秀的深紫外非线性光学晶体。但由于KBBF是一种层状结构的晶体，层与层之间是靠静电吸引而不是通过价键相连接的，层状习性严重，在z方向生长速度很慢，生长出的单晶体分层现象明显，晶体不易生长。
SBBO的基本结构基元也是(BO 3) 3-平面基团，但它用氧取代氟离子，使得层与层之间通过氧桥相互连接，以便改进KBBF的层状习性，而每一层的结构则保持基本不变。SBBO不仅具有较大的宏观倍频系数，低的紫外吸收边(165nm)，适中的双折射率(Δn＝0.06)，而且彻底克服了晶体的层状习性，解决了晶体生长的问题。在此基础上，保持(BO 3) 3-基团的结构条件基本不变，替换阳离子Sr 2+和Be原子，相继研制了TBO、KABO、BABO等一系列非线性光学晶体，它们统称为SBBO族晶体。它们克服了KBBF单晶生长的层状习性，但这些晶体到目前为止还不能取代KBBF单晶，因为TBO晶体的结构完整性不好，其宏观性能显示的光学均匀性非常差，目前还无法在实际器件中得到应用；KABO和BABO晶体的结构完整性很好，具有较好的光学均匀性，但由于Al取代了Be，它们的吸收边红移到180nm左右，很难用于深紫外的谐波输出。
LBO的基本结构基元是将(B 3O 6) 3-基团中的一个B原子由三配位变成四配位从而形成(B 3O 7) 5-基团。它具有较大的倍频系数，紫外吸收边在160nm左右，但是由于在实际晶体内的(B 3O 7) 5-基团互相连接，在空间中形成与z轴成45°的螺旋链而无法在晶格中平行排列，使晶体的双折射率降得过低(Δn＝0.04～0.05)，从而使得它在紫外区的相位匹配范围受到严重限制，使带隙宽的优势未能充分发挥。
因此，开发各方面性能均十分优秀的紫外和深紫外非线性光学晶体 材料，已成为当前非线性光学材料研究领域的难点和前沿方向之一。
发明内容
为克服现有技术的不足，本发明提供一种碱金属氰尿酸一氢盐化合物，其化学式为AM(HC 3N 3O 3)·nH 2O，其中，A、M相同或不同，彼此独立地选自碱金属，例如Li、Na、K、Rb、Cs、Fr；n选自0以上的整数。
优选地，n选自0-10的整数，例如0、1、2、3、4、5、6、7、8、9、10，优选为2。
根据本发明的实施方案，所述化合物可以选自二水合氰尿酸一氢钾锂(化学式：KLi(HC 3N 3O 3)·2H 2O；简称KLHCY)、二水合氰尿酸一氢铷锂(化学式：RbLi(HC 3N 3O 3)·2H 2O；简称RLHCY)、二水合氰尿酸一氢铷钠(化学式：RbNa(HC 3N 3O 3)·2H 2O；简称RNHCY)。
根据本发明，所述化合物可以为非线性光学晶体形式。
本发明还提供一种二水合氰尿酸一氢钾锂非线性光学晶体，其化学式为KLi(HC 3N 3O 3)·2H 2O。
根据本发明，所述二水合氰尿酸一氢钾锂非线性光学晶体具有基本上如图3所示的X射线粉末衍射图谱。
根据本发明，所述二水合氰尿酸一氢钾锂非线性光学晶体不具有对称中心，属于正交晶系，空间群为Pna2(1)，晶胞参数为
Figure PCTCN2018098122-appb-000001
Figure PCTCN2018098122-appb-000002
α＝β＝γ＝90°，Z＝4，单胞体积为
Figure PCTCN2018098122-appb-000003
Figure PCTCN2018098122-appb-000004
本发明还提供一种二水合氰尿酸一氢铷锂非线性光学晶体，其化学式为RbLi(HC 3N 3O 3)·2H 2O。
根据本发明，所述二水合氰尿酸一氢铷锂非线性光学晶体具有基本上如图4所示的X射线粉末衍射图谱。
根据本发明，所述二水合氰尿酸一氢铷锂非线性光学晶体不具有对称中心，属于正交晶系，空间群为Pna2(1)，晶胞参数为
Figure PCTCN2018098122-appb-000005
Figure PCTCN2018098122-appb-000006
α＝β＝γ＝90°，Z＝4，单胞体积为
Figure PCTCN2018098122-appb-000007
Figure PCTCN2018098122-appb-000008
本发明还提供一种二水合氰尿酸一氢铷钠非线性光学晶体，其化学式为RbNa(HC 3N 3O 3)·2H 2O。
根据本发明，所述二水合氰尿酸一氢铷钠非线性光学晶体具有基本上如图5所示的X射线粉末衍射图谱。
根据本发明，所述二水合氰尿酸一氢铷钠非线性光学晶体不具有对称中心，属于正交晶系，晶空间群为Pna2(1)，晶胞参数为
Figure PCTCN2018098122-appb-000009
Figure PCTCN2018098122-appb-000010
α＝β＝γ＝90°，Z＝4，单胞体积为
Figure PCTCN2018098122-appb-000011
本发明还提供上述碱金属氰尿酸一氢盐化合物的制备方法，包括将AOH·xH 2O、MOH·yH 2O、与H 3C 3N 3O 3进行反应，得到碱金属氰尿酸一氢盐化合物；其中，A、M具有上文所述的定义；x、y相同或不同，彼此独立地选自0以上的整数。
优选地，x、y相同或不同，彼此独立地选自0-10的整数，例如0、1、2、3、4、5、6、7、8、9、10，优选为0、1。
根据本发明，所述AOH·xH 2O、MOH·yH 2O与H 3C 3N 3O 3的摩尔比可以为(0.5～2.5):(0.5～2.5):1，优选为(0.8～1.2):(0.8～1.2):1，例如1:1:1。
所述反应可以在溶剂中进行，所述溶剂可以选自有机溶剂或无机溶剂，优选为无机溶剂，例如水；
原料总质量与溶剂的比例可以为5～50g原料/100ml溶剂，优选为10～30g原料/100ml溶剂；
所述反应的温度可以为50～110℃，优选为60～100℃，例如80℃；
根据本发明，反应结束后，可以将反应液以恒定的降温速率进行降温；降温后，用溶剂进行清洗，即可获得碱金属氰尿酸一氢盐化合物；
根据本发明，降温速率为1～10℃/小时，优选为1～5℃/小时，例如1℃/小时、5℃/小时；
根据本发明，反应液降温至0～40℃，优选为10～40℃，例如10℃、40℃；
清洗使用的溶剂为水、丙酮或其混合物，可以采用上述溶剂分多次进行清洗；优选地，清洗使用的溶剂为丙酮。
根据本发明，使用上述方法制备得到的是晶体，所述晶体的体积大于2.0mm 3。
本发明还提供上述碱金属氰尿酸一氢盐化合物(例如晶体)的用途，其可用于激光器激光输出的频率变换、紫外区的谐波发生器、光参量与放大器件及光波导器件；
优选地，所述化合物可以对波长为1.064μm的激光光束产生2倍频或3倍频或4倍频或5倍频或6倍频的谐波光输出；
优选地，所述化合物可以用于从红外到紫外区的光参量与放大器件。
本发明的有益效果：
本发明提供了化学式为AM(HC 3N 3O 3)·nH 2O(具体如KLi(HC 3N 3O 3)·2H 2O、RbLi(HC 3N 3O 3)·2H 2O、RbNa(HC 3N 3O 3)·2H 2O)的碱金属氰尿酸一氢盐化合物及其非线性光学晶体，该非线性光学晶体具有极强的相位匹配能力(使用粉末倍频测试方法测量，其粉末倍频效应约为KH 2PO 4(KDP)的2-3倍)；其紫外吸收边短于250nm。另外，该非线性光学晶体能够实现Nd:YAG(λ＝1.064μm)的2倍频、3倍频、4倍频的谐波发生器。并且，该非线性光学晶体为单晶结构，无色透明，在空气中不潮解。所以可以预见，AM(HC 3N 3O 3)·nH 2O(具体如 KLi(HC 3N 3O 3)·2H 2O、RbLi(HC 3N 3O 3)·2H 2O、RbNa(HC 3N 3O 3)·2H 2O)将在各种非线性光学领域中获得广泛应用，并将开拓紫外波段的非线性光学应用。
附图说明
图1是KLHCY、RLHCY、RNHCY晶体作为倍频晶体应用时非线性光学效应的典型示意图，其中1是激光器，2是入射激光束，3是经晶体后处理及光学加工的单晶体，4是所产生的出射激光束，5是滤波片。
图2是KLHCY、RLHCY、RNHCY晶体的结构示意图(KLHCY、RLHCY、RNHCY为同构化合物)。
图3是KLHCY单晶研磨成粉末后的X射线衍射图谱。
图4是RLHCY单晶研磨成粉末后的X射线衍射图谱。
图5是RNHCY单晶研磨成粉末后的X射线衍射图谱。
具体实施方式
如上所述，本发明提供了一种全新结构的化合物及其晶体，其结构式为AM(HC 3N 3O 3)·nH 2O(具体如KLHCY、RLHCY、RNHCY)，其中的氰尿酸一氢根为晶体生长提供了优秀的水溶液生长性能以及非线性性能。
下文将结合具体实施例对本发明做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。
实施例1
采用水溶液法制备KLi(HC 3N 3O 3)·2H 2O、RbLi(HC 3N 3O 3)·2H 2O和RbNa(HC 3N 3O 3)·2H 2O单晶
Figure PCTCN2018098122-appb-000012
具体操作步骤如下：将上述原料按上述剂量称好后，装入100ml的烧杯中，放入一个磁子，把烧杯放到磁力加热搅拌器，将烧杯边搅拌边升温至80℃，然后以5℃每小时的降温速率降温至40℃。冷却后将样品用丙酮洗净，即可获得大小为5×1×1mm的KLi(HC 3N 3O 3)·2H 2O单晶。
制备RbLi(HC 3N 3O 3)·2H 2O单晶所用原料：
Figure PCTCN2018098122-appb-000013
具体操作步骤如下：将上述原料按上述剂量称好后，装入100ml的烧杯中，放入一个磁子，把烧杯放到磁力加热搅拌器，将烧杯边搅拌边升温至80℃，然后以5℃每小时的降温速率降温至40℃。冷却后将样品用丙酮洗净，即可获得大小为1×1×5mm的RbLi(HC 3N 3O 3)·2H 2O单晶。
制备RbNa(HC 3N 3O 3)·2H 2O单晶所用原料：
Figure PCTCN2018098122-appb-000014
具体操作步骤如下：将上述原料按上述剂量称好后，装入100ml的 烧杯中，放入一个磁子，把烧杯放到磁力加热搅拌器，将烧杯边搅拌边升温至80℃，然后以5℃每小时的降温速率降温至10℃。冷却后将样品用丙酮洗净，即可获得大小为1×5×1mm的RbNa(HC 3N 3O 3)·2H 2O单晶。
实施例2
采用水溶液法制备KLi(HC 3N 3O 3)·2H 2O、RbLi(HC 3N 3O 3)·2H 2O和RbNa(HC 3N 3O 3)·2H 2O单晶
Figure PCTCN2018098122-appb-000015
具体操作步骤如下：将上述原料按上述剂量称好后，装入100ml的烧杯中，放入一个磁子，把烧杯放到磁力加热搅拌器，将烧杯边搅拌边升温至80℃，然后以1℃每小时的降温速率降温至40℃。冷却后将样品用丙酮洗净，即可获得大小为5×2×2mm的KLi(HC 3N 3O 3)·2H 2O单晶。
制备RbLi(HC 3N 3O 3)·2H 2O单晶所用原料：
Figure PCTCN2018098122-appb-000016
具体操作步骤如下：将上述原料按上述剂量称好后，装入100ml的烧杯中，放入一个磁子，把烧杯放到磁力加热搅拌器，将烧杯边搅拌边升温至80℃，然后以1℃每小时的降温速率降温至40℃。冷却后将样品用丙酮洗净，即可获得大小为2×2×5mm的RbLi(HC 3N 3O 3)·2H 2O单晶。
制备RbNa(HC 3N 3O 3)·2H 2O单晶所用原料：
Figure PCTCN2018098122-appb-000017
Figure PCTCN2018098122-appb-000018
具体操作步骤如下：将上述原料按上述剂量称好后，装入100ml的烧杯中，放入一个磁子，把烧杯放到磁力加热搅拌器，将烧杯边搅拌边升温至80℃，然后以1℃每小时的降温速率降温至10℃。冷却后将样品用丙酮洗净，即可获得大小为2×5×2mm的RbNa(HC 3N 3O 3)·2H 2O单晶。
实施例3
将实施例2得到的KLi(HC 3N 3O 3)·2H 2O、RbLi(HC 3N 3O 3)·2H 2O和RbNa(HC 3N 3O 3)·2H 2O晶体，加工切割，定向，抛光后置于图1所示装置中的3的位置，在室温下，用调Q Nd:YAG激光做输入光源，入射波长为1064nm，观察到明显的532nm倍频绿光输出，输出强度约为同等条件KDP的2-3倍。具体地，KLi(HC 3N 3O 3)·2H 2O晶体的输出强度约为同等条件KDP的3倍，RbLi(HC 3N 3O 3)·2H 2O晶体的输出强度约为同等条件KDP的2倍，RbNa(HC 3N 3O 3)·2H 2O晶体的输出强度约为同等条件KDP的2倍。
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种碱金属氰尿酸一氢盐化合物，其特征在于，所述化合物的化学式为AM(HC 3N 3O 3)·nH 2O，其中，A、M相同或不同，彼此独立地选自碱金属，例如Li、Na、K、Rb、Cs、Fr；n选自0以上的整数。
  2. 根据权利要求1所述的化合物，其特征在于，n选自0-10的整数，例如0、1、2、3、4、5、6、7、8、9、10，具体例如2。
  3. 根据权利要求1或2所述的化合物，其特征在于，所述化合物选自二水合氰尿酸一氢钾锂(化学式：KLi(HC 3N 3O 3)·2H 2O)、二水合氰尿酸一氢铷锂(化学式：RbLi(HC 3N 3O 3)·2H 2O)或二水合氰尿酸一氢铷钠(化学式：RbNa(HC 3N 3O 3)·2H 2O)；
    优选地，所述化合物为非线性光学晶体形式。
  4. 根据权利要求1-3任一项所述的化合物，其特征在于，所述化合物为二水合氰尿酸一氢钾锂非线性光学晶体，所述晶体的化学式为KLi(HC 3N 3O 3)·2H 2O；
    优选地，所述二水合氰尿酸一氢钾锂非线性光学晶体具有基本上如图3所示的X射线粉末衍射图谱；
    优选地，所述二水合氰尿酸一氢钾锂非线性光学晶体不具有对称中心，属于正交晶系，空间群为Pna2(1)，晶胞参数为
    Figure PCTCN2018098122-appb-100001
    Figure PCTCN2018098122-appb-100002
    α＝β＝γ＝90°，Z＝4，单胞体积为
    Figure PCTCN2018098122-appb-100003
    Figure PCTCN2018098122-appb-100004
  5. 根据权利要求1-3任一项所述的化合物，其特征在于，所述化合物为二水合氰尿酸一氢铷锂非线性光学晶体，所述晶体的化学式为RbLi(HC 3N 3O 3)·2H 2O；
    优选地，所述二水合氰尿酸一氢铷锂非线性光学晶体具有基本上如 图4所示的X射线粉末衍射图谱；
    优选地，所述二水合氰尿酸一氢铷锂非线性光学晶体不具有对称中心，属于正交晶系，空间群为Pna2(1)，晶胞参数为
    Figure PCTCN2018098122-appb-100005
    Figure PCTCN2018098122-appb-100006
    α＝β＝γ＝90°，Z＝4，单胞体积为
    Figure PCTCN2018098122-appb-100007
    Figure PCTCN2018098122-appb-100008
  6. 根据权利要求1-3任一项所述的化合物，其特征在于，所述化合物为二水合氰尿酸一氢铷钠非线性光学晶体，所述晶体的化学式为RbNa(HC 3N 3O 3)·2H 2O；
    优选地，所述二水合氰尿酸一氢铷钠非线性光学晶体具有基本上如图5所示的X射线粉末衍射图谱；
    优选地，所述二水合氰尿酸一氢铷钠非线性光学晶体不具有对称中心，属于正交晶系，晶空间群为Pna2(1)，晶胞参数为
    Figure PCTCN2018098122-appb-100009
    Figure PCTCN2018098122-appb-100010
    α＝β＝γ＝90°，Z＝4，单胞体积为
    Figure PCTCN2018098122-appb-100011
    Figure PCTCN2018098122-appb-100012
  7. 权利要求1-6任一项所述化合物的制备方法，其特征在于，所述制备方法包括将AOH·xH 2O、MOH·yH 2O、与H 3C 3N 3O 3进行反应，得到碱金属氰尿酸一氢盐化合物；其中，A、M具有权利要求1所述的定义；x、y相同或不同，彼此独立地选自0以上的整数。
  8. 根据权利要求7所述的制备方法，其特征在于，所述x、y相同或不同，彼此独立地选自0-10的整数，例如0、1、2、3、4、5、6、7、8、9、10，如0、1；
    优选地，所述AOH·xH 2O、MOH·yH 2O与H 3C 3N 3O 3的摩尔比为(0.5～2.5):(0.5～2.5):1，优选为(0.8～1.2):(0.8～1.2):1，例如1:1:1；
    优选地，所述反应在溶剂中进行，所述溶剂选自有机溶剂或无机溶剂，优选为无机溶剂，例如水；
    优选地，所述反应的温度为50～110℃，优选为60～100℃，例如80℃。
  9. 根据权利要求7或8所述的制备方法，其特征在于，反应结束后，将反应液以恒定的降温速率进行降温；降温后，用溶剂进行清洗，即获得碱金属氰尿酸一氢盐化合物；
    优选地，降温速率为1～10℃/小时，优选为1～5℃/小时，例如1℃/小时、5℃/小时；
    优选地，反应液降温至0～40℃，优选为10～40℃，例如10℃、40℃；
    优选地，清洗使用的溶剂为水、丙酮或其混合物，例如丙酮。
  10. 权利要求1-6任一项所述化合物的用途，其特征在于，所述化合物可用于激光器激光输出的频率变换、紫外区的谐波发生器、光参量与放大器件及光波导器件；
    优选地，所述化合物对波长为1.064μm的激光光束产生2倍频或3倍频或4倍频或5倍频或6倍频的谐波光输出；
    优选地，所述化合物用于从红外到紫外区的光参量与放大器件。
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