CN101984152B - Nonlinear optical crystal of dimalic acid ammonium borate monohydrate compound and growing method and application thereof - Google Patents
Nonlinear optical crystal of dimalic acid ammonium borate monohydrate compound and growing method and application thereof Download PDFInfo
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- CN101984152B CN101984152B CN2010105533786A CN201010553378A CN101984152B CN 101984152 B CN101984152 B CN 101984152B CN 2010105533786 A CN2010105533786 A CN 2010105533786A CN 201010553378 A CN201010553378 A CN 201010553378A CN 101984152 B CN101984152 B CN 101984152B
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Abstract
The present invention relates to a kind of compounds one to be hydrated two malic acid boron ammonium nonlinear optical crystals and its growing method and purposes, the compound chemical formula is NH4B (C4H4O5) 2H2O, belong to rhombic system, space group is Pna21, molecular weight is 311.01, and cell parameter is a=11.484 (6)
B=5.354 (3)
C=21.079 (12)
Crystal is obtained using water soluble method, resulting crystal is easily grown up and more transparent, and the nonlinear optical effect of the crystal is about 1.5 times of KDP, is had than wider transmission region. The crystal has many advantages, such as that at low cost, easy to operate, the speed of growth is fast, toxicity is low, better mechanical property, hardness are larger. The crystal available extensive use in the device for non-linear optical such as frequency-doubled conversion, optical parametric oscillator.
Description
Technical field
The present invention relates to a kind of compound one hydration two malic acid boron ammonium nonlinear optical crystals, this crystal-chemical formula is NH
4B (C
4H
4O
5)
2H
2O, the device for non-linear optical that utilizes this crystal to make.
Background technology
The major function of non-linear optical crystal material is frequency conversion, is mainly used in laser freuqency doubling and frequency, difference frequency, aspects such as frequency multiplication, parametric oscillation and amplification repeatedly.Through the frequency conversion effect of non-linear optical crystal material, can produce new optical maser wavelength to the output wavelength of certain laser instrument at new frequency place, thereby create an approach for producing new laser emission, widened the range of application of laser.
The research of early stage nonlinear optical material mainly concentrates on mineral crystal and semiconductor material section, has manyly obtained practical application, like crystal such as quartz, KDP, KTP, LN, BBO, LBO, CBO.Though the crystal technique of these materials reaches its maturity, but still exist weak point separately.
The people such as Renzepis of the U.S. in 1964 have at first found the nonlinear optical effect of organic compound, and are that nonlinear optical material has been opened up a new field.Organic compound has the advantage that many inorganic material do not possess as nonlinear optical material, as: the NLO coefficient ratio of organic material has obtained and practical mineral crystal such as the high 1-2 one magnitude of LN; The response of organic material is fast; The optical damage value of cutting off from is higher; Better machining property etc. is arranged.In addition, their costs are relatively low, can change mechanical development and go out new structural material through MOLECULE DESIGN and synthetic method.Organic NLO material of finding at present or synthesizing is a lot, and typical second order NLO crystal has urea and derivant thereof, azo-compound etc.
In the last few years, the research to the nonlinear optical crystal of hybrid inorganic-organic compound had become the research topic that quite is concerned by people in this field.Compare with pure organic compound, the hybrid inorganic-organic compound has diversified structure and better thermal stability, simultaneously as nonlinear optical material, has the nonlinear optical coefficients higher than mineral compound mostly again.Therefore this quasi-nonlinear optical crystal has often combined inorganic and the advantage organic compound nonlinear optical crystal.Therefore, utilize the hybrid inorganic-organic compound form various, advantages such as easy cutting are the important method of exploring and develop the novel molecular based non-linear optical crystal material with application prospect.
Summary of the invention
The object of the invention is to provide a kind of compound one hydration two malic acid boron ammonium nonlinear optical crystals, and chemical formula is NH
4B (C
4H
4O
5)
2H
2O.
Another object of the present invention is to provide the preparation method of compound one hydration two malic acid boron ammonium nonlinear optical crystals.
Still a further object of the present invention is to provide the purposes of compound one hydration two malic acid boron ammonium nonlinear optical crystals.
Hybrid inorganic-organic compound one hydration two malic acid boron ammoniums of the present invention, this compound chemistry formula is NH
4B (C
4H
4O
5)
2H
2O belongs to orthorhombic system, and space group is Pna21, and molecular weight is 311.01, and cell parameter is a=11.484 (6)
B=5.354 (3)
C=21.079 (12)
The preparation method of described compound one hydration two malic acid boron ammonium nonlinear optical crystals adopts aqua-solution method to prepare crystal, and concrete operations follow these steps to carry out:
A, boric acid or diboron trioxide and malic acid are dissolved in the 10-100mL deionized water, then incomplete dissolved substances are handled 30min with ultrasound wave down at 40 ℃, make its abundant mixed dissolution;
B, the solution among the step a naturally cooled to room temperature after, add ammoniacal liquor and regulate the pH value to 2-5;
C, the solution among the step b is sealed with pan paper, under temperature of reaction 20-40 ℃, left standstill 30-70 days;
D, treat that step c solution grows crystal grain in the bottom of container, no longer include significant change until crystal size, growth ending, the solution that will contain crystal filters, and obtains the transparent crystal of a hydration two malic acid boron ammoniums;
The saturated aqueous solution of e, preparation boric acid or diboron trioxide and malic acid is used ultrasonic Treatment 30min, again the saturated solution that obtains is regulated the pH value to 2-5 with ammoniacal liquor;
F, select in the steps d quality preferably crystal as seed crystal; It is hung in the saturated solution of step e preparation; At temperature 20-40 ℃ of following constant temperature, or, can obtain having the large scale one hydration two malic acid boron ammonium transparent crystals of centimetre-sized to reduce to room temperature through 1-5 ℃/day rate of temperature fall.
The mol ratio of the raw material that adds among the step a is a boric acid: malic acid=1: 2-4 or diboron trioxide: malic acid=1: 4-8.
Used malic acid is L (+)-malic acid, D (-)-malic acid or DL-malic acid among the step a.
The addition of ammoniacal liquor is confirmed by the pH value among step b and the step e, both has been reactant, is again the pH value correctives of system.
In the environment that the solution of step c is placed on is clean, pollution-free, air does not have convection current.
Described compound one hydration two malic acid boron ammonium nonlinear optical crystals are as the purposes of preparation frequency multiplication generator.
The used method of the present invention is an aqua-solution method, after being about to initiation material and proportionally mixing, regulates the pH value with ammoniacal liquor, in certain temperature range, obtain crystal through slow volatilization moisture after, select then quality preferably seed crystal hang on the H that regulated the pH value with ammoniacal liquor
3BO
3Or B
2O
3In the saturated aqueous solution of malic acid, a transparent hydration two malic acid boron ammonium nonlinear optical crystals that the method through constant temperature or the method for slowly cooling can obtain having the centimetre-sized size.
The preparation method of compound one hydration two malic acid boron ammonium nonlinear optical crystals according to the invention uses H
3BO
3Or B
2O
3Press 1 with malic acid: 2-4 mixes, and regulates the pH value with ammoniacal liquor and carries out combination reaction.
Below be severally typically can obtain NH
4B (C
4H
4O
5)
2H
2The chemical reaction of O:
(1)H
3BO
3+H
2O+NH
3·H
2O+L(+)-C
4H
6O
5→NH
4B(L(+)-C
4H
4O
5)
2·H
2O+H
2O
(2)H
3BO
3+H
2O+NH
3·H
2O+D(-)-C
4H
6O
5→NH
4B(D(-)-C
4H
4O
5)
2·H
2O+H
2O
(3)H
3BO
3+H
2O+NH
3·H
2O+DL-C
4H
6O
5→NH
4B(DL-C
4H
4O
5)
2·H
2O+H
2O
(4)B
2O
3+H
2O+NH
3·H
2O+L(+)-C
4H
6O
5→NH
4B(L(+)-C
4H
4O
5)
2·H
2O+H
2O
(5)B
2O
3+H
2O+NH
3·H
2O+D(-)-C
4H
6O
5→NH
4B(D(-)-C
4H
4O
5)
2·H
2O+H
2O
(6)B
2O
3+H
2O+NH
3·H
2O+DL-C
4H
6O
5→NH
4B(DL-C
4H
4O
5)
2·H
2O+H
2O
The compound that uses among the present invention can adopt commercially available reagent and raw material, and crystal is prone to grow up and is transparent, have simple to operate, fast growth, growth cycle is short, cost is low, obtains advantages such as large-size crystals easily.
NH provided by the present invention
4B (C
4H
4O
5)
2H
2The O crystal does not have specific (special) requirements to the optics machining precision.
Description of drawings
Fig. 1 is an XRD spectra of the present invention;
Fig. 2 is crystallogram figure of the present invention;
Fig. 3 is the repetitive figure of structure of the present invention;
Fig. 4 is the fundamental diagram of the device for non-linear optical of the present invention's making; Comprising 1 is laser instrument; 2 is convex lens, and 3 is a hydration two malic acid boron ammonium nonlinear optical crystals, and 4 is Amici prism; 5 is filter plate, and ω equals incident light frequency or incident light frequency 2 times for the refraction light frequency.
Embodiment
Embodiment 1
With chemical reaction H
3BO
3+ H
2O+NH
3H
2O+L (+)-C
4H
6O
5→ NH
4B (L (+)-C
4H
4O
5)
2H
2O+H
2O prepares a hydration two malic acid boron ammonium nonlinear optical crystals.
Took by weighing H in 1: 2 in molar ratio
3BO
3And L (+)-malic acid is dissolved in the container that fills the 10mL deionized water, then incomplete dissolved substances used ultrasonic Treatment 30min at 40 ℃, makes its abundant mixed dissolution;
Solution is taken out, naturally cool to room temperature, add ammoniacal liquor and regulate pH to 2;
Seal with pan paper, solution is placed in the environment clean, pollution-free, that air does not have convection current, temperature of reaction is 20 ℃, leaves standstill 30 days;
After 30 days, there are some less crystal to form, treat that crystal continues to grow up, do not have significant change until crystal size in the bottom of container, growth ending, the solution that will contain crystal filters, and obtains a hydration two malic acid boron ammonium transparent crystals;
Prepared boric acid and L (+)-malic acid saturated aqueous solution in 1: 2 in molar ratio, handle 30min down for 40 ℃, the saturated solution that obtains is added ammoniacal liquor regulate pH to 2 with ultrasound wave;
Selection quality crystal preferably hangs on it in above saturated solution as seed crystal, reduces to room temperature through 1 ℃/day rate of temperature fall, can obtain a hydration two malic acid boron ammonium crystal of centimetre-sized.
Embodiment 2:
With reaction equation H
3BO
3+ H
2O+NH
3H
2O+D (-)-C
4H
6O
5→ NH
4B (D (-)-C
4H
4O
5)
2H
2O+H
2O prepares a hydration two malic acid boron ammonium nonlinear optical crystals:
Took by weighing H in 1: 3 in molar ratio
3BO
3And D (-)-malic acid is dissolved in the container that fills the 30mL deionized water, then incomplete dissolved substances used ultrasonic Treatment 30min at 40 ℃, makes its abundant mixed dissolution;
Solution is taken out, naturally cool to room temperature, add ammoniacal liquor and regulate pH to 2.5;
Seal with pan paper, solution is placed in the environment clean, pollution-free, that air does not have convection current, temperature of reaction is 30 ℃, leaves standstill 43 days;
After 43 days, there are some less crystal to form, treat that crystal continues to grow up, do not have significant change until crystal size in the bottom of container, growth ending, the solution that will contain crystal filters, and obtains a hydration two malic acid boron ammonium transparent crystals;
Prepared boric acid and D (-)-malic acid saturated aqueous solution in 1: 3 in molar ratio, handle 30min down for 40 ℃, again the saturated solution that obtains is added ammoniacal liquor and regulate pH to 2.5 with ultrasound wave;
Selection quality crystal preferably hangs on it in above saturated solution as seed crystal, reduces to room temperature through 3 ℃/day rate of temperature fall, can obtain a hydration two malic acid boron ammonium crystal of centimetre-sized.
Embodiment 3:
With chemical equation H
3BO
3+ H
2O+NH
3H
2O+DL-C
4H
6O
5→ NH
4B (DL-C
4H
4O
5)
2H
2O+H
2O prepares a hydration two malic acid boron ammonium nonlinear optical crystals:
Took by weighing H in 1: 4 in molar ratio
3BO
3Be dissolved in the container that fills the 50mL deionized water with the DL-malic acid, then incomplete dissolved substances used ultrasonic Treatment 30min at 40 ℃, make its abundant mixed dissolution;
Solution is taken out, naturally cool to room temperature, add ammoniacal liquor and regulate pH to 3;
Seal with pan paper, solution is placed in the environment clean, pollution-free, that air does not have convection current, temperature of reaction is 40 ℃, leaves standstill 51 days;
After 51 days, there are some less crystal to form, treat that crystal continues to grow up, do not have significant change until crystal size in the bottom of container, growth ending, the solution that will contain crystal filters, and obtains a hydration two malic acid boron ammonium transparent crystals;
Prepared boric acid and DL-malic acid saturated aqueous solution in 1: 4 in molar ratio, handle 30min down for 40 ℃, again the saturated solution that obtains is added ammoniacal liquor and regulate pH to 3 with ultrasound wave;
Selection quality crystal preferably hangs on it in above saturated solution as seed crystal, reduces to room temperature through 5 ℃/day rate of temperature fall, can obtain a hydration two malic acid boron ammonium crystal of centimetre-sized.
Embodiment 4:
With chemical reaction B
2O
3+ H
2O+L (+)-C
4H
6O
5→ NH
4B (L (+)-C
4H
4O
5)
2H
2O+H
2O prepares a hydration two malic acid boron ammonium nonlinear optical crystals:
Took by weighing B in 1: 4 in molar ratio
2O
3And L (+)-malic acid is dissolved in the container that fills the 70mL deionized water, then incomplete dissolved substances used ultrasonic Treatment 30min at 40 ℃, makes its abundant mixed dissolution;
Solution is taken out, naturally cool to room temperature, add ammoniacal liquor and regulate pH to 3.5;
Seal with pan paper, solution is placed in the environment clean, pollution-free, that air does not have convection current, temperature of reaction is 20 ℃, leaves standstill 70 days;
After 70 days, there are some less crystal to form, treat that crystal continues to grow up, do not have significant change until crystal size in the bottom of container, growth ending, the solution that will contain crystal filters, and obtains a hydration two malic acid boron ammonium transparent crystals;
1: 2 in molar ratio preparation B
2O
3And L (+)-malic acid saturated aqueous solution, handle 30min down for 40 ℃ with ultrasound wave, again the saturated solution that obtains is added ammoniacal liquor and regulate pH to 3.5;
Selection quality crystal preferably hangs on it in above saturated solution as seed crystal, and temperature of reaction is at 20 ℃, leaves standstill 35 days, can obtain a hydration two malic acid boron ammonium crystal of centimetre-sized.
Embodiment 5:
With chemical reaction B
2O
3+ H
2O+D (-)-C
4H
6O
5→ NH
4B (D (-)-C
4H
4O
5)
2H
2O+H
2O prepares a hydration two malic acid boron ammonium nonlinear optical crystals:
Took by weighing B in 1: 6 in molar ratio
2O
3And D (-)-malic acid is dissolved in the container that fills the 90mL deionized water, then incomplete dissolved substances used ultrasonic Treatment 30min at 40 ℃, makes its abundant mixed dissolution;
Solution is taken out, naturally cool to room temperature, add ammoniacal liquor and regulate pH to 4;
Seal with pan paper, solution is placed in the environment clean, pollution-free, that air does not have convection current, temperature of reaction is 30 ℃, leaves standstill 64 days;
After 64 days, there are some less crystal to form, treat that crystal continues to grow up, do not have significant change until crystal size in the bottom of container, growth ending, the solution that will contain crystal filters, and obtains a hydration two malic acid boron ammonium transparent crystals;
1: 6 in molar ratio preparation B
2O
3And D (-)-malic acid saturated aqueous solution, handle 30min down for 40 ℃ with ultrasound wave, again the saturated solution that obtains is added ammoniacal liquor and regulate pH to 4;
Selection quality crystal preferably hangs on it in above saturated solution as seed crystal, and temperature of reaction is at 30 ℃, leaves standstill 27 days, can obtain a hydration two malic acid boron ammonium crystal of centimetre-sized.
Embodiment 6:
With chemical equation B
2O
3+ H
2O+NH
3H
2O+DL-C
4H
6O
5→ NH
4B (DL-C
4H
4O
5)
2H
2O+H
2O prepares a hydration two malic acid boron ammonium nonlinear optical crystals:
Took by weighing B in 1: 8 in molar ratio
2O
3Be dissolved in the container that fills the 100mL deionized water with the DL-malic acid, then incomplete dissolved substances used ultrasonic Treatment 30min at 40 ℃, make its abundant mixed dissolution;
Solution is taken out, naturally cool to room temperature, add ammoniacal liquor and regulate pH to 5;
Seal with pan paper, solution is placed in the environment clean, pollution-free, that air does not have convection current, temperature of reaction is 40 ℃, leaves standstill 59 days;
After 59 days, there are some less crystal to form, treat that crystal continues to grow up, do not have significant change until crystal size in the bottom of container, growth ending, the solution that will contain crystal filters, and obtains a hydration two malic acid boron ammonium transparent crystals;
1: 8 in molar ratio preparation B
2O
3And D (-)-malic acid saturated aqueous solution, handle 30min down for 40 ℃ with ultrasound wave, again the saturated solution that obtains is added ammoniacal liquor and regulate pH to 5;
Selection quality crystal preferably hangs on it in above saturated solution as seed crystal, and temperature of reaction is at 40 ℃, leaves standstill 28 days, and a hydration two malic acid boron ammonium crystal that can obtain centimetre-sized close two malic acid boron ammonium transparent crystals;
Embodiment 7:
With the crystal of any one gained among the embodiment 1-6, by being placed on the position of (3), at room temperature shown in the accompanying drawing 3; Light source is made in 1064nm output with transferring Q Nd:YAG laser instrument; Observe the output of tangible 532nm frequency multiplication green glow, output intensity is suitable with equal conditions KDP, shown in Figure 3ly does; By transferring Q Nd:YAG laser instrument 1 to send wavelength is that the infrared beam of 1064nm is injected a hydration two malic acid boron ammonium nonlinear optical crystals through convex lens 2; Producing wavelength is the green frequency doubled light of 532nm, and it is the infrared light of 1064nm and the green glow of 532nm that outgoing beam 4 contains wavelength, after filter plate 5 eliminations, obtains the frequency doubled light that wavelength is 532nm.
Claims (6)
1. hybrid inorganic-organic compound one hydration two malic acid boron ammonium nonlinear optical crystals is characterized in that this compound chemistry formula is NH
4B (C
4H
4O
5)
2H
2O belongs to orthorhombic system, and space group is Pna2
1, molecular weight is 311.01, cell parameter does
2. the preparation method of compound one hydration two malic acid boron ammonium nonlinear optical crystals according to claim 1 is characterized in that adopting aqua-solution method to prepare crystal, and concrete operations follow these steps to carry out:
A, boric acid or diboron trioxide and malic acid are dissolved in the 10-100mL deionized water; Then incomplete dissolved substances is used ultrasonic Treatment 30min; Make its abundant mixed dissolution, the mol ratio of the raw material that wherein adds is a boric acid: malic acid=1: 2-4 or diboron trioxide: malic acid=1: 4-8;
B, the solution among the step a naturally cooled to room temperature after, add ammoniacal liquor and regulate the pH value to 2-5;
C, the solution among the step b is sealed with pan paper, under temperature of reaction 20-40 ℃, left standstill 30-70 days;
D, treat that step c solution grows crystal grain in the bottom of container, no longer include significant change until crystal size, growth ending, the solution that will contain crystal filters, and obtains the transparent crystal of a hydration two malic acid boron ammoniums;
The saturated aqueous solution of e, preparation boric acid or diboron trioxide and malic acid is used ultrasonic Treatment 30min, again the saturated solution that obtains is regulated the pH value to 2-5 with ammoniacal liquor;
F, select in the steps d quality preferably crystal as seed crystal; It is hung in the saturated solution of step e preparation; At temperature 20-40 ℃ of following constant temperature 15-35 days or with the cooling of 1-5 ℃/day speed, can obtain having the large-sized hydration of centimetre-sized two malic acid boron ammonium transparent crystals.
3. method according to claim 2 is characterized in that malic acid used among the step a is L (+)-malic acid, D (-)-malic acid or DL-malic acid.
4. method according to claim 2 is characterized in that the addition of ammoniacal liquor among step b and the step e is confirmed by the pH value, both has been reactant, is again the pH value correctives of system.
5. method according to claim 2 is characterized in that the solution of step c is placed in the environment clean, pollution-free, that air does not have convection current.
6. compound one hydration two malic acid boron ammonium nonlinear optical crystals according to claim 1 is characterized in that the purposes of this crystal as preparation frequency multiplication generator.
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| CN104250845B (en) * | 2013-06-27 | 2017-05-03 | 中国科学院化学研究所 | Construction method of low-dimensional organic frequency-doubling crystal |
| CN103351379B (en) * | 2013-07-04 | 2014-10-22 | 华侨大学 | Growing method of second-order nonlinear laser material N, N'-propionyl-(2-thenoyl) hydrazine crystal |
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| US4839536A (en) * | 1987-11-24 | 1989-06-13 | Regents Of The University Of Minnesota | Optically nonlinear pyridine-N-oxide complexes |
| DE69017243T2 (en) * | 1989-03-29 | 1995-10-12 | Rockwell International Corp | Semi-organic crystals for non-linear optical devices. |
| CN1811490A (en) * | 2005-01-24 | 2006-08-02 | 北京师范大学 | Class I organic-inorganic hybridized Second-order non-linear optical thin film material |
| CN1866119A (en) * | 2006-06-19 | 2006-11-22 | 浙江大学 | Inorganic-organic hybridized non-linear optical film and preparation method thereof |
| CN100489638C (en) * | 2006-10-24 | 2009-05-20 | 南京工业大学 | Preparation of organic non-linear optical material L malic acid derivative crystal |
| CN101446735B (en) * | 2008-12-01 | 2010-06-30 | 中国科学院新疆理化技术研究所 | Nonlinear optical material of strontium-ammonium boron tartrate tetrahydrate and preparation method and application thereof |
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