阅读说明：本技术 化合物氟碘酸锶和氟碘酸锶紫外非线性光学晶体及制备方法和用途 (Compound strontium fluoiodate and strontium fluoiodate ultraviolet nonlinear optical crystal, preparation method and application ) 是由 潘世烈 盖敏强 于 2020-06-02 设计创作，主要内容包括：本发明涉及一种化合物氟碘酸锶和氟碘酸锶紫外非线性光学晶体及制备方法和用途,该化合物的化学式为Sr(IO<Sub>2</Sub>F<Sub>2</Sub>)<Sub>2</Sub>·2H<Sub>2</Sub>O,分子量为517.45,采用水热法制成,其结构为无色透明晶体,该晶体的化学式为Sr(IO<Sub>2</Sub>F<Sub>2</Sub>)<Sub>2</Sub>·2H<Sub>2</Sub>O,分子量为517.45,属于正交晶系,P2<Sub>1</Sub>2<Sub>1</Sub>2<Sub>1</Sub>(No.19),晶胞参数为a=7.849(5)?,b=8.158(5)?,c=13.863(9)?；V=887.6(10)?<Sup>3</Sup>,Z＝4,采用水热法,通过程序降温或恒温的方法即得到毫米级的透明的氟碘酸锶紫外非线性光学晶体,该晶体具有操作简单、成本低、所用的试剂为无机原料、生长周期短、物化性质稳定等优点,在倍频转换、光参量振荡器等非线性光学器件中得到广泛应用。(The invention relates to a compound strontium fluoiodate, a strontium fluoiodate ultraviolet nonlinear optical crystal, a preparation method and application thereof, wherein the chemical formula of the compound is Sr (IO) 2 F 2 ) 2 ·2H 2 O, molecular weight of 517.45, and is prepared by hydrothermal method, and the structure is colorless transparent crystal with chemical formula of Sr (IO) 2 F 2 ) 2 ·2H 2 O, molecular weight 517.45, belonging to orthorhombic system, P2 1 2 1 2 1 (No.19) unit cell parameters a =7.849(5) Å, b =8.158(5) Å, c =13.863(9) Å; V =887.6(10) Å 3 The Z is 4, the hydrothermal method is adopted, and the millimeter-grade transparent strontium fluoiodate ultraviolet nonlinear optical crystal is obtained by a programmed cooling or constant temperature method, and the crystal has the advantages of simple operation and low costThe used reagent is inorganic material, has short growth period and stable physical and chemical properties, and may be used widely in frequency doubling conversion, optical parametric oscillator and other non-linear optical devices.)

1. A compound strontium fluoiodate is characterized in that the chemical formula of the compound is Sr (IO)₂F₂)₂·2H₂O, molecular weight 517.45, prepared by hydrothermal method, and is colorless transparent crystal.

2. Strontium fluoroiodate ultraviolet nonlinear lightA chemical crystal characterized in that the chemical formula of the crystal is Sr (IO)₂F₂)₂·2H₂O, molecular weight 517.45, space group P2₁2₁2₁(No.19) unit cell parameters a =7.849(5) Å, b =8.158(5) Å, c =13.863(9) Å; unit cell volume 887.6(10) ų，Z＝4。

3. The method for preparing strontium fluoroiodate ultraviolet nonlinear optical crystal as claimed in claim 2, characterized by adopting hydrothermal method, and the concrete operation is carried out according to the following steps:

a. putting a strontium-containing compound and an iodine-containing compound into a mortar according to the mol ratio of 0.3-4:1-3 or the mol ratio of the strontium-containing compound to the iodine-containing compound to the fluorine-containing compound of 0.3-1:1:0.5-3, uniformly mixing and fully grinding the mixture, adding 0.2-2ml of a mineralizer, adding 0.2-5ml of the mineralizer, adding a mixed solution of fluoride and deionized water with the mass fraction of 40%, or adding 0.2-5ml of fluoride with the mass fraction of 40%, and fully dissolving the mixture to obtain a mixture, wherein the strontium-containing compound is strontium iodate, strontium carbonate, strontium nitrate or strontium acetate, the iodine-containing compound is iodic acid or strontium iodate, the mineralizer is phosphoric acid, hydrofluoric acid or fluoroboric acid, and the fluoride is one or two of ammonium fluoride, hydrofluoric acid and fluoroboric acid;

b, filling the mixture obtained in the step a into a polytetrafluoroethylene lining of a high-pressure hydrothermal reaction kettle with the volume of 50mL, screwing and sealing the hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant temperature box, heating to 180-220 ℃ at the heating rate of 10-30 ℃/h, keeping the temperature for 1-5 days, then cooling to room temperature at the heating rate of 1-10 ℃/h, opening the hydrothermal reaction kettle, and cleaning the obtained product by using deionized water or absolute ethyl alcohol to obtain the colorless and transparent strontium fluoiodate ultraviolet nonlinear optical crystal.

4. Use of the strontium fluoroiodate ultraviolet nonlinear optical crystal as claimed in claim 2 in preparation of frequency doubling generators and optical parametric oscillators.

Technical Field

The invention relates to a compound strontium fluoiodate, a strontium fluoiodate ultraviolet nonlinear optical crystal, a preparation method and application thereof, wherein the strontium fluoiodate belongs to the field of inorganic nonmetallic materials and the field of optics.

Background

The second-order nonlinear optical crystal is an important novel photoelectric functional material and has important application value in the fields of laser frequency conversion, modulation of laser intensity and phase, photoelectric communication, optical information processing and the like. The second-order nonlinear optical crystal which is currently put into practical use comprises LiB₃O₅(LBO),β-BaB₂O₄(BBO)，KH₂PO₄(KDP)，KTiOPO₄(KTP)，LiNbO₃(LNO)，BaTiO₃(BTO)，α-LiIO₃，KIO₃And the like. With the development of laser technology and the emergence of tunable lasers, nonlinear optical devices develop rapidly, and laser frequency doubling, frequency mixing, parametric oscillation and amplification are achieved; electro-optical modulation, deflection, Q-switching, and photorefractive devices, etc. occur sequentially. The research and application mentioned above put more and higher requirements on the physical and chemical properties of the nonlinear optical material, and also promote the rapid development of the nonlinear optical material. The inorganic groups giving rise to noncardial structures predominantly comprise BO₃ ^3-、PO₄ ^3-、CO₃ ^3-、IO₃ ^3-And NO₃ ^-A plasma of anionic groups and lone pair-containing cationic ions (e.g., I (V), Se (IV), Bi (III), Pb (II), Te (IV), etc.) and distorted octahedral coordination d⁰Electron configuration transition metal cations (e.g., Ti (IV), V (V), Nb (V), Ta (V), Mo (VI), W (VI), etc.). The metal iodate crystal has stronger frequency doubling effect, wider transmission waveband, higher thermal stability and optical damage threshold, and plays a very important role in the field of second-order nonlinear optical crystal materials.

The application further widens the research of the iodate system, and synthesizes strontium fluoiodate (Sr (IO) by introducing alkaline earth metal strontium and fluorine₂F₂)₂·2H₂O), the crystal is a novel nonlinear optical crystal material. The test shows that: the second-order nonlinear optical effect of the crystal is about 2 times KDP, and the ultraviolet transmission cut-off edge is 245 nm. Therefore, the strontium fluoiodate crystal is expected to be used as a novel nonlinear optical crystal material to obtain corresponding variable frequency laser output with higher efficiency, thereby obtaining practical application。

Disclosure of Invention

The invention aims to provide a compound strontium fluoiodate, wherein the chemical formula of the compound is Sr (IO)₂F₂)₂·2H₂O, molecular weight of 545.94, and preparing the strontium fluoiodate compound by a hydrothermal method.

Another object of the present invention is to provide a strontium fluoroiodate UV nonlinear optical crystal characterized by that its chemical formula is Sr (IO)₂F₂)₂·2H₂O, space group of the crystal is P2₁2₁2₁(No.19) having unit cell parameters of Unit cell volume ofZ-4, molecular weight 517.45.

The invention further aims to provide a method for preparing and growing strontium fluoiodate ultraviolet nonlinear optical crystal by a hydrothermal method.

The invention also aims to provide the application of the strontium fluoiodate nonlinear optical crystal in preparing a frequency doubling generator and an optical parametric oscillator.

The chemical formula of the compound strontium fluoiodate is Sr (IO)₂F₂)₂·2H₂O₈Molecular weight is 517.45, and the structure is colorless transparent crystal prepared by hydrothermal method.

A strontium fluoroiodate ultraviolet non-linear optical crystal has a chemical formula of Sr (IO)₂F₂)₂·2H₂O, molecular weight 517.45, space group P2₁2₁2₁(No.19), unit cell parameters Cell volumeZ＝4。

The preparation method of the strontium fluoiodate ultraviolet nonlinear optical crystal adopts a hydrothermal method, and comprises the following specific operations:

a. putting a strontium-containing compound and an iodine-containing compound into a mortar according to the mol ratio of 0.3-4:1-3 or the mol ratio of the strontium-containing compound to the iodine-containing compound to the fluorine-containing compound of 0.3-1:1:0.5-3, uniformly mixing and fully grinding the mixture, adding 0.2-2ml of a mineralizer, adding 0.2-5ml of the mineralizer, adding a mixed solution of fluoride and deionized water with the mass fraction of 40%, or adding 0.2-5ml of fluoride with the mass fraction of 40%, and fully dissolving the mixture to obtain a mixture, wherein the strontium-containing compound is strontium iodate, strontium carbonate, strontium nitrate or strontium acetate, the iodine-containing compound is iodic acid or strontium iodate, the mineralizer is phosphoric acid, hydrofluoric acid or fluoroboric acid, and the fluoride is one or two of ammonium fluoride, hydrofluoric acid and fluoroboric acid;

b, filling the mixture obtained in the step a into a polytetrafluoroethylene lining of a high-pressure hydrothermal reaction kettle with the volume of 50mL, screwing and sealing the hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant temperature box, heating to 180-220 ℃ at the heating rate of 10-30 ℃/h, keeping the temperature for 1-5 days, then cooling to room temperature at the heating rate of 1-10 ℃/h, opening the hydrothermal reaction kettle, and cleaning the obtained product by using deionized water or absolute ethyl alcohol to obtain the colorless and transparent strontium fluoiodate ultraviolet nonlinear optical crystal.

The strontium fluoroiodate ultraviolet nonlinear optical crystal is used for preparing a frequency doubling generator and an optical parametric oscillator.

The compound strontium fluoiodate and strontium fluoiodate ultraviolet nonlinear optical crystal, the preparation method and the application thereof are disclosed, wherein SrCO₃、HIO₃、H₃PO₄The raw materials for the reaction with HF can adopt reagents and raw materials sold in the market, and the crystal is extremely easy to grow and is transparent, so that the method has the advantages of simple operation, high growth speed, low cost, easy obtainment of large-size crystals and the like.

Drawings

FIG. 1 is a powder X-ray diffraction pattern of the present invention;

FIG. 2 is a crystal structure of the present invention;

fig. 3 is a schematic diagram of the operation of the nonlinear optical device according to the present invention, which includes (1) a laser, (2) a holographic lens, (3) a strontium fluoiodate nonlinear optical crystal, (4) a beam splitter prism, and (5) a filter, wherein ω is the frequency of the refracted light equal to or 2 times the frequency of the incident light.

Detailed Description

The invention is described in detail below with reference to the following figures and examples: