CN103710749A - Sodium calcium fluorocarbonate compound and nonlinear optical crystal thereof, and crystal growth method - Google Patents

Sodium calcium fluorocarbonate compound and nonlinear optical crystal thereof, and crystal growth method Download PDF

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CN103710749A
CN103710749A CN201310690859.5A CN201310690859A CN103710749A CN 103710749 A CN103710749 A CN 103710749A CN 201310690859 A CN201310690859 A CN 201310690859A CN 103710749 A CN103710749 A CN 103710749A
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calcium carbonate
crystal
carbonate sodium
optic crystal
linear optic
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叶宁
罗敏
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

A kind of novel nonlinear optical crystal fluorine calcium carbonate sodium, chemical formula are Ca2Na3 (CO3) 3F(abbreviation CNCF). Its crystal structure belongs to monoclinic system, space group Cm, and cell parameter is
Figure DDA0000439187440000011
Figure DDA0000439187440000012
α=γ=90 °, β=101.662 °, z=2, unit-cell volume are
Figure DDA0000439187440000014
Its Clock Multiplier Factor is KH2PO4(KDP) 4 times. Its ultraviolet absorption edge is shorter than 200nm. The monocrystalline of CNCF compound is obtained under subcritical water heat condition using hydrothermal synthesis method. Ca2Na3 (CO3) 3F has nonlinear optical effect, the nonlinear optics application that can be used widely in various non-linear optical fields, and will open up deep ultraviolet band.

Description

Fluorine calcium carbonate sodium compound and non-linear optic crystal thereof and growing method
Technical field
The present invention relates to a kind of photoelectron functional materials and growth method and purposes, particularly relate to a kind of non-linear optical crystal material and its production and use, i.e. fluorine calcium carbonate sodium, its chemical formula is Ca 2na 3(CO 3) 3f, is called for short CNCF.
Technical background
The non-linear optical effect of crystal refers to a kind of like this effect: when a branch of laser with certain polarization direction passes through a non-linear optic crystal (as CNCF) by certain incident direction, the frequency of this light beam will change.
The crystal with non-linearity optical effect is called non-linear optic crystal.Utilize non-linear optic crystal to carry out laser frequency conversion, widen the scope of optical maser wavelength, make the application of laser more extensive.Especially borate family non-linear optic crystal receives much attention with its excellent optical property as crystal such as BBO, LBO, KBBF, SBBO, TBO, KABO, BABO.Development in photo-optics, photoengraving, precision instrument processing and other fields more and more needs ultraviolet and deep ultraviolet laser coherent source, needs ultraviolet and the deep ultraviolet nonlinear optical crystal of excellent performance.
The basic structure primitive of KBBF is (BO 3) 3-plane group, the ultraviolet absorption edge of this crystal, in about 155nm, has moderate degree of birefringence (Δ n=0.07), can realize very wide phase matched scope, is classic deep ultraviolet nonlinear optical crystal so far.But because KBBF is a kind of crystal of laminate structure, by electrostatic attraction rather than be connected by valence link, stratiform habit is serious, very slow in the z direction speed of growth between layers, and the single crystal demixing phenomenon growing is obvious, and crystal is difficult for growth.
The basic structure primitive of SBBO is also (BO 3) 3-plane group, but it replaces fluorion with oxygen, makes by oxo bridge, to interconnect between layers, and to improve the stratiform habit of KBBF, it is substantially constant that the structure of every one deck keeps.SBBO not only has larger macroscopical Clock Multiplier Factor, low ultraviolet absorption edge (165nm), and moderate degree of birefringence (Δ n=0.06), and thoroughly overcome the stratiform habit of crystal, solved the problem of crystal growth.On this basis, keep (BO 3) 3-the structural condition of group is substantially constant, replaces kation S r 2+with Be atom, in succession developed a series of non-linear optic crystals such as TBO, KABO, BABO, they are referred to as SBBO group crystal.They have overcome the stratiform habit of KBBF single crystal growing, but up to the present these crystal can't replace KBBF monocrystalline, because the structural integrity of SBBO and TBO crystal is bad, the non-constant of optical homogeneity that its macro property shows also cannot be applied at present in practical devices; The structural integrity of KABO and BABO crystal is fine, has good optical homogeneity, but because Al has replaced Be, their ABSORPTION EDGE red shift, to 180nm left and right, is difficult to the harmonic wave of deep ultraviolet.
Due to (CO 3) 2-with (BO 3) 3-structure similar with ligancy, we think available (CO 3) 2-replace (BO 3) 3-, then using alkali and alkaline earth metal ions ion as positively charged ion, add fluorion to adjust interlayer structure, thereby obtain new compound, the application of developing deep ultraviolet nonlinear optical crystal.Through hydrothermal crystal growth, single crystal structure determination, has confirmed that this imagination is possible.
Summary of the invention
The object of the present invention is to provide a kind of fluorine calcium carbonate sodium compound, its chemical formula is Ca 2na 3(CO 3) 3f.
Another object of the present invention is to provide a kind of fluorine calcium carbonate sodium compound preparation method.
Another object of the present invention is to provide a kind of fluorine calcium carbonate sodium non-linear optic crystal, its chemical formula is Ca 2na 3(CO 3) 3f.
A further object of the present invention is to provide a kind of growth method of fluorine calcium carbonate sodium non-linear optic crystal.
A further object of the invention is to provide the purposes of fluorine calcium carbonate sodium non-linear optic crystal.
Technical scheme of the present invention is as follows:
Fluorine calcium carbonate sodium compound provided by the invention, its chemical formula is Ca 2na 3(CO 3) 3f.
Fluorine calcium carbonate sodium non-linear optic crystal provided by the invention, its chemical formula is Ca 2na 3(CO 3) 3f, this crystal does not have symmetry centre, belongs to oblique system, and spacer is Cm, unit cell parameters
Figure BDA0000439187420000021
α=γ=90 °, β=101.662 °, z=2, unit-cell volume is
Figure BDA0000439187420000023
Figure BDA0000439187420000024
crystalline structure is as Fig. 2.
The growth method of fluorine calcium carbonate sodium non-linear optic crystal provided by the invention, its step is as follows: with Na 2cO 3for mineralizer growth, NaF:Na 2cO 3: CaCl 2=3:5:1, raw material is mixed according to the above ratio and puts into water heating kettle, be warming up to 220 ℃, after constant temperature 5～7 days, with 3 ℃ of rate of temperature fall hourly, be cooled to 30 ℃, take out water and alcohol and clean, obtain fluorine calcium carbonate sodium non-linear optic crystal of the present invention, be of a size of 0.5 * 0.4 * 0.3mm.The raw materials of compound adopting is for containing the fluorochemical of sodium and muriate, the Na of carbonate and calcic 2cO 3naF and CaCl 2.The lenticular fluorine calcium carbonate sodium obtaining, then grind into powder, carry out XRD detection to it, and result is as Fig. 3.
The purposes of fluorine calcium carbonate sodium non-linear optic crystal provided by the invention, this non-linear optic crystal fluorine calcium carbonate sodium is for the frequency transformation of laser device laser output.
The purposes of fluorine calcium carbonate sodium non-linear optic crystal provided by the invention, this crystal produces 2 frequencys multiplication for the laser beam that is 1.064 μ m to wavelength, 3 frequencys multiplication, 4 frequencys multiplication, the humorous glistening light of waves output of 5 frequencys multiplication.
The purposes of fluorine calcium carbonate sodium non-linear optic crystal provided by the invention, this crystal is the humorous glistening light of waves output lower than 200nm for generation of wavelength.
The purposes of fluorine calcium carbonate sodium non-linear optic crystal provided by the invention, described non-linear optic crystal is the harmonic generator for ultraviolet region, optical parameter and amplifying device and fiber waveguide device.
The purposes of fluorine calcium carbonate sodium non-linear optic crystal provided by the invention, described non-linear optic crystal is optical parameter and the amplifying device from infrared to ultraviolet region.
It is Ca that effect of the present invention is to provide a kind of chemical formula 2na 3(CO 3) 3the compound of F, non-linear optic crystal of this compound and its production and use.Use powder frequency doubling testing method to measure Ca 2na 3(CO 3) 3the phase matched ability of F, the Clock Multiplier Factor that its powder SHG effect is it is KH 2pO 4(KDP) 4 times.Its ultraviolet absorption edge is shorter than 200nm.Ca 2na 3(CO 3) 3f crystal can be realized Nd:YAG(λ=1.064 μ m) 2 frequencys multiplication, and, can predict Ca 2na 3(CO 3) 3f can be used in 3 frequencys multiplication, 4 frequencys multiplication of Nd:YAG, the harmonic generator of 5 frequencys multiplication, even for generation of the humorous glistening light of waves output shorter than 200nm.In addition, Ca 2na 3(CO 3) 3f monocrystalline water white transparency, deliquescence not, chemical stability is good.So can predict Ca 2na 3(CO 3) 3f will obtain widespread use in various non-linear optical fields, and by the nonlinear optics application of developing deep ultraviolet wave band.
Accompanying drawing explanation
Fig. 1 is Ca 2na 3(CO 3) 3f crystal is as the canonical schema of frequency-doubling crystal application non-linear hour optical effect, and wherein 1 is laser apparatus, and the 2nd, incoming laser beam, the 3rd, through the Ca of crystal aftertreatment and optics processing 2na 3(CO 3) 3f single crystal, the 4th, the outgoing laser beam producing, the 5th, filter plate.
Fig. 2 is Ca 2na 3(CO 3) 3f crystal unit cell structural representation.
Fig. 3 is Ca 2na 3(CO 3) 3the x ray diffraction collection of illustrative plates of F, Fig. 3 is Ca 2na 3(CO 3) 3the F monocrystalline last diffractogram of pulverizing.
Embodiment
Embodiment 1
Adopt hydro-thermal reaction growth Ca 2na 3(CO 3) 3f monocrystalline
Raw materials used: Na 2cO 31.06 grams (0.01mol)
0.252 gram of NaF (0.006mol)
CaCl 20.222 gram (0.002mol)
Concrete operation step is as follows: after in operation box, above-mentioned raw materials being weighed up by above-mentioned dosage, put into that mortar mixes and carefully grind, then pack in the water heating kettle of 23ml, pour the distilled water of 5mL into, water heating kettle is put in baking oven, baking oven is slowly warming up to 220 ℃, and constant temperature 7 days, is then cooled to 30 ℃ with 3 ℃ of rate of temperature fall hourly.After cooling, samples with water and alcohol are cleaned, can be obtained Ca 2na 3(CO 3) 3f size is the monocrystalline of 0.5 * 0.4 * 0.3mm.
Embodiment 2
Adopt hydro-thermal reaction growth Ca 2na 3(CO 3) 3f monocrystalline
Raw materials used: Na 2cO 310.6 grams (0.1mol)
2.52 grams of NaF (0.06mol)
CaCl 22.22 grams (0.02mol)
Concrete operation step is as follows: after in operation box, above-mentioned raw materials being weighed up by above-mentioned dosage, put into that mortar mixes and carefully grind, then pack in the water heating kettle of 200ml, pour the distilled water of 50mL into, water heating kettle is put in baking oven, baking oven is slowly warming up to 220 ℃, and constant temperature 7 days, is then cooled to 30 ℃ with 3 ℃ of rate of temperature fall hourly.After cooling, samples with water and alcohol are cleaned, can be obtained Ca 2na 3(CO 3) 3f size is the monocrystalline of 3 * 2 * 2.5mm.
Embodiment 3
The crystal that example 2 is obtained, processing cutting, orientation, polishing is placed on the position of 3 in Fig. 1 shown device, at room temperature, and with adjusting Q Nd:YAG laser to do input light source, incident wavelength is 1064nm, observes obvious 532nm frequency doubling green light output, and output intensity is about 4 times of equal conditions KDP.

Claims (9)

1. compound fluorine calcium carbonate sodium, is characterized in that: its chemical formula is Ca 2na 3(CO 3) 3f, belongs to oblique system, and spacer is Cm, and unit cell parameters is
Figure FDA0000439187410000011
α=γ=90 °, β=101.662 °, z=2, unit-cell volume is
Figure FDA0000439187410000012
2. a preparation method for the fluorine calcium carbonate sodium compound of claim 1, is characterized in that: after the raw materials of compound containing Ca, Na, F and C is evenly mixed by suitable proportion, put into water heating kettle, be slowly warmed up to after 220 ℃ constant temperature 5～7 days; Be cooled to room temperature, take out water and alcohol and clean, can obtain fluorine calcium carbonate sodium compound.
3. compound fluorine calcium carbonate sodium claimed in claim 1 is a kind of non-linear optic crystal.
4. a growth method for fluorine calcium carbonate sodium non-linear optic crystal claimed in claim 3, adopts Hydrothermal Growth, it is characterized in that: with Na 2cO 3for mineralizer, NaF:Na 2cO 3: CaCl 2=3:5:1, mixes raw material according to the above ratio and puts into water heating kettle, is warming up to 220 ℃, after constant temperature 5-7 days, then by the speed of 3～5 ℃ per hour, is cooled to 50 ℃, closes stove; After sample is cooled to room temperature, water and alcohol are cleaned, and obtain the fluorine calcium carbonate sodium non-linear optic crystal that is of a size of 0.5 * 0.4 * 0.3mm.
5. a purposes for fluorine calcium carbonate sodium non-linear optic crystal claimed in claim 3, is characterized in that: this non-linear optic crystal is for the frequency transformation of laser device laser output.
6. a purposes for fluorine calcium carbonate sodium non-linear optic crystal claimed in claim 5, is characterized in that: this crystal produces the humorous glistening light of waves output of 2 frequencys multiplication or 3 frequencys multiplication or 4 frequencys multiplication or 5 frequencys multiplication for the laser beam that is 1.064 μ m to wavelength.
7. a purposes for fluorine calcium carbonate sodium non-linear optic crystal claimed in claim 5, is characterized in that: this crystal is the humorous glistening light of waves output lower than 200nm for generation of wavelength.
8. a purposes for fluorine calcium carbonate sodium non-linear optic crystal claimed in claim 5, is characterized in that: described non-linear optic crystal is the harmonic generator for ultraviolet region, optical parameter and amplifying device and fiber waveguide device.
9. a purposes for fluorine calcium carbonate sodium non-linear optic crystal claimed in claim 5, is characterized in that: described non-linear optic crystal is optical parameter and amplifying device from infrared to ultraviolet region.
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CN113293440A (en) * 2021-05-08 2021-08-24 中国科学院福建物质结构研究所 Preparation method and application of potassium lithium malonate monohydrate compound and nonlinear optical crystal thereof
CN115044976A (en) * 2021-03-09 2022-09-13 中国科学院理化技术研究所 Second-order nonlinear optical crystal and preparation method and application thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115044976A (en) * 2021-03-09 2022-09-13 中国科学院理化技术研究所 Second-order nonlinear optical crystal and preparation method and application thereof
CN115044976B (en) * 2021-03-09 2024-04-12 中国科学院理化技术研究所 Second-order nonlinear optical crystal and preparation method and application thereof
CN113293440A (en) * 2021-05-08 2021-08-24 中国科学院福建物质结构研究所 Preparation method and application of potassium lithium malonate monohydrate compound and nonlinear optical crystal thereof

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