CN103351379A - Second-order nonlinear laser material N, N'-propionyl-(2-thenoyl) hydrazine crystal and growing method and application thereof - Google Patents
Second-order nonlinear laser material N, N'-propionyl-(2-thenoyl) hydrazine crystal and growing method and application thereof Download PDFInfo
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Abstract
The invention provides a second-order nonlinear laser material N, N'-propionyl-(2-thenoyl) hydrazine crystal and the growing method and application thereof. The crystal belongs to a orthorhombic crystal system, the space group of the crystal is P2<1>2<1>2<1>, Mr equals to 1988.24, the crystallography parameter is as follows: a equals to 9.344 angstroms, b equals to 9.395 angstroms, c equals to 11.370 angstroms, V equals to 998.0 cubic angstrom and Z equals to 4, and a molecule of N, N'-propionyl-(2-thenoyl) hydrazine is formed by an N-(2-thenoyl) hydrazino plane and a propiono plane which are perpendicular; the growing method comprises the following steps: propiono is introduced onto N-(2-thenoyl) hydrazine, then the produced isomer of N, N'-propionyl-(2-thenoyl) hydrazine is dissolved in the chloroform and methyl alcohol mixed solvent and evaporated till saturation under the room temperature, the saturated isomer solution of N, N'-propionyl-(2-thenoyl) hydrazine is placed in a cuvette, and 36-volt direct voltage is applied to the isomer solution, the isomer solution is evaporated, the seed crystal is produced, then the solution is transferred to a culture groove, and the chloroform and methyl alcohol mixed solvent is evaporated so as to obtain the columnar crystal, namely the N, N'-propionyl-(2-thenoyl) hydrazine crystal.
Description
[technical field]
The present invention relates to two-order nonlinear laser material N, N '-propionyl-(2-thenoyl) hydrazine crystal and growth method and application.
[background technology]
When light wave is propagated in nonlinear dielectric, can cause non linear electrodes, cause the nonlinear interaction between the light wave, the nonlinear interaction between the light wave that high-intensity laser causes is more obvious.In second order frequency multiplication process, in a single day fundamental frequency light inject non-linear optic crystal, and the each position on light path all will produce the secondary polarized wave, and these polarized waves are all launched the with it second harmonic of same frequency, or be called the frequency multiplication light wave.
At present, the two-order nonlinear laser material that uses both at home and abroad mainly contains following several:
1, potassium primary phosphate (KDP), its light wave interaction type is: ooe, m=41 ° of phase matching angle θ, efficiency of conversion 81%.
2, potassium dideuterium phosphate (DKDP), its light wave interaction type is: eoe, m=53.5 ° of phase matching angle θ, efficiency of conversion 50%.
3, (α-LiIO3), its light wave interaction type is alpha-lithium iodate: ooe, m=30 ° of phase matching angle θ, efficiency of conversion 50%.
4, potassium titanium oxide phosphate (KTP), its light wave interaction type is: eoe, m=30 ° of phase matching angle θ, efficiency of conversion 50%.
5, barium metaborate (BBO), its light wave interaction type is: ooe, m=21 ° of phase matching angle θ, efficiency of conversion 70%.
It more than is mineral crystal, because the nonlinear optical coefficients of organic crystal are usually than large 1-2 the order of magnitude of mineral crystal, and optical homogeneity is good, growth apparatus is easy, people have done many researchs to organic compound polycrystal powder frequency-doubled effect, some novel, efficient organic nonlinear optical crystals have been found, following table is several more typical examples: 3-methyl-4-nitropyridine-N-oxygen (POM), 2,4-dinitrobenzene amido methyl propionate (MAP), m-N-methyl-p-nitroaniline (m-NA), 2-methyl-4-nitrophenylamine (MNA).
Table 1Nd
3+: the SHG (1064--532nm) of YAG laser radiation organic double-frequency crystal
But most of organic crystalline physique are soft, and fusing point is low, and degree of birefringence is too large, thereby their application is restricted.
The inventor had once developed growth method (the molecular formula C of a kind of second-order non-linear laser crystal body 4-nitro-N-oxygen-2-pyridine carboxylic acid two generation crystals
6H
4N
2O
5, be called for short POA-II), see Chinese invention patent number: ZL200710008940.5,2009-11-25,162.5-163.5 ℃ of its crystalline melting point is better than POM, frequency-doubled effect d
Eff/ d
KDP=9.8, with the same order of magnitude of POM, specific refractory power calculating value n
Max=1.6807, n
Min=1.5465, Δ n=0.1342 is better than POM, but the inventor is still satisfied to its fusing point, satisfies and continues research and development, has eventually this case to produce.
[summary of the invention]
The technical problem to be solved in the present invention, be to provide a kind of two-order nonlinear laser material N, N '-propionyl-(2-thenoyl) hydrazine crystal and growth method and application, this crystalline melting point reaches 175.5～176.5 ℃, and can be used for wavelength is that the laser of 1064nm is converted to 532nm.
The present invention is achieved in that
A kind of two-order nonlinear laser material N, N '-propionyl-(2-thenoyl) hydrazine crystal, described N, N '-propionyl-(2-thenoyl) hydrazine crystal belongs to rhombic system, and spacer is P2
12
12
1, molecular formula C
8H
10N
2O
2S, Mr=1988.24, crystallographic parameter:
Z=4, N, N '-propionyl-(2-thenoyl) hydrazine molecule is made of the gentle propionyl of vertical each other N-(2-thenoyl) diazanyl plane.
Described two-order nonlinear laser material N, the growth method of N '-propionyl-(2-thenoyl) hydrazine is as follows:
Introduce propionyl at N-(2-thenoyl) hydrazine; then with the N that generates; the isomer of N '-propionyl-(2-thenoyl) hydrazine is dissolved in the imitative pure mixed solvent; and chloroform in the described imitative pure mixed solvent: methyl alcohol=1: 1; and under room temperature, be evaporated to saturated; take out saturated N; the ppolymorphism liquid solution of N '-propionyl-(2-thenoyl) hydrazine places cuvette; apply the volts DS of 36V in the cuvette outside; evaporation grows seed crystal, then seed crystal is transferred to culture tank; same imitative pure mixed solvent evaporation obtains styloid N, N '-propionyl-(2-thenoyl) hydrazine.
Further, described N, the isomer crystal of N '-propionyl-(2-thenoyl) hydrazine belongs to triclinic(crystalline)system, and spacer is P-1, molecular formula C
8H
10N
2O
2S, Mr=1988.24, crystallographic parameter:
α=70.00 °, β=88.58 °, γ=71.11 °,
Z=6 is without the second order frequency-doubled effect.
Further, described N, N '-propionyl-(2-thenoyl) hydrazine crystal is converted to 532nm for the laser that with wavelength is 1064nm.
The present invention has following advantage:
The present invention introduces propionyl to improve its physical strength and thermostability (fusing point) at N-(2-thenoyl) hydrazine.N of the present invention, the fusing point of N '-propionyl-(2-thenoyl) hydrazine crystal is high, reaches 175.5-176.5 ℃, obviously is better than POA-II (162.5-163.5 ℃) and POM, 1064nm laser freuqency doubling effect d
Eff/ d
KDP=9.6, with POA-II and the same order of magnitude of POM, specific refractory power calculating value n
Max=1.7586, n
Min=1.6264, Δ n=0.1322, close with POA-II, be better than POM (calculated value n
Max=1.7891, n
Min=1.6217, Δ n=0.1674), uv-visible absorption spectra is measured and is shown that maximum absorption band is at 223nm, and transparency range is more than the 350-800nm.
[description of drawings]
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is N of the present invention, the differential thermal analysis (DSC) of N '-propionyl-(2-thenoyl) hydrazine crystal and thermogravimetric analysis (TGA) Thermogram.
Fig. 2 is N of the present invention, differential thermal analysis (DSC) and thermogravimetric analysis (TGA) Thermogram of N '-propionyl-(2-thenoyl) hydrazine crystal isomer.
Fig. 3 is N of the present invention, the solid diffuse-reflectance uv-visible absorption spectra figure of N '-propionyl-(2-thenoyl) hydrazine crystal.
[embodiment]
See also shown in Fig. 1～3, embodiments of the invention are described in detail.
The present invention relates to a kind of two-order nonlinear laser material N, N '-propionyl-(2-thenoyl) hydrazine crystal, described N, N '-propionyl-(2-thenoyl) hydrazine crystal belongs to rhombic system, and spacer is P2
12
12
1, molecular formula C
8H
10N
2O
2S, Mr=1988.24, crystallographic parameter:
Z=4, N, N '-propionyl-(2-thenoyl) hydrazine molecule is made of the gentle propionyl of vertical each other N-(2-thenoyl) diazanyl plane.
The invention still further relates to described two-order nonlinear laser material N, the growth method of N '-propionyl-(2-thenoyl) hydrazine, and the method is as follows:
Introduce propionyl at N-(2-thenoyl) hydrazine; then with the N that generates; the isomer of N '-propionyl-(2-thenoyl) hydrazine is dissolved in the imitative pure mixed solvent; and chloroform in the described imitative pure mixed solvent: methyl alcohol=1: 1; and under room temperature, be evaporated to saturated; take out saturated N; the ppolymorphism liquid solution of N '-propionyl-(2-thenoyl) hydrazine places cuvette; apply the volts DS of 36V in the cuvette outside; evaporation grows seed crystal, then seed crystal is transferred to culture tank; same imitative pure mixed solvent evaporation obtains styloid N, N '-propionyl-(2-thenoyl) hydrazine.
Described N, the isomer crystal of N '-propionyl-(2-thenoyl) hydrazine belongs to triclinic(crystalline)system, and spacer is P-1, molecular formula C
8H
10N
2O
2S, Mr=1988.24, crystallographic parameter:
α=70.00 °, β=88.58 °, γ=71.11 °,
Z=6 is without the second order frequency-doubled effect.
Described N, N '-propionyl-(2-thenoyl) hydrazine crystal is converted to 532nm for the laser that with wavelength is 1064nm.
The applicant is for convenient elaboration the present invention, and with above-mentioned N, N '-propionyl-(2-thenoyl) hydrazine crystal names with the PTHZ crystal; With N, the ppolymorphism body and function tPTHZ crystal of N '-propionyl-(2-thenoyl) hydrazine crystal is named.
The present invention is further illustrated below in conjunction with embodiment.
Embodiment
1, preparation thiophene ethyl formate
Take by weighing 7g (0.05mol) thiophenic acid in the 250ml flask, add 30ml (0.5mol) anhydrous alcohol solution, slowly splash into the 9ml vitriol oil; Heat to 120 ℃ at the heat-collecting magnetic stirring device and refluxed 12 hours, then unnecessary ethanol is removed in underpressure distillation, and then with the extraction of 45ml water, the ester that obtains is by Na
2CO
3Saturated solution is washed till neutrality; Add anhydrous Na
2SO
4Drying, underpressure distillation after filtering obtains colourless transparent liquid 4.4g, and productive rate is 51.6%.
2, preparation thiophene hydrazides
Above-mentioned thiophene ethyl formate in molar ratio 1:1.5 add 85% hydrazine hydrate 2.2ml, be heated to about 110 ℃ and refluxed 2 hours, place refrigerator overnight, the adularescent needle-like solid is separated out, and washs with frozen water behind the suction filtration; Obtain fusing point and be 132 ℃ white fluffy needle-like crystal 0.4g, productive rate 10% changes 85% hydrazine hydrate into the anhydrous hydrazine productive rate and reaches 94%.
3, preparation PTHZ crystal
Take by weighing 1g (7mmol) thiophene hydrazides, be dissolved in about 50ml chloroform, under ice bath stirs, slowly splash into 1ml (7mmol) propionic anhydride; Continuation stirring reaction after 10 minutes in ice bath, at room temperature naturally volatilize a week, the mixed solution of separating out solid carried out the isomer that suction filtration obtains the faint yellow transparent crystallite tPTHZ(PTHZ of 1.17g), productive rate 83.9%, fusing point 175.5-176.5 ℃, as shown in Figure 2.
4, the crystal of PTHZ growth
TPTHZ is dissolved in the imitative pure mixed solvent, and its volume ratio is chloroform: methyl alcohol=1: 1 is evaporated near saturated under the room temperature (25 ℃), take out an amount of nearly saturated tPTHZ solution and place quartz colorimetric utensil, the cuvette outside applies the volts DS of 36V, and slow evaporation grew seed crystal after 3 days; To being equipped with in the nearly saturated tPTHZ water culture groove, slow evaporation under the room temperature obtains the column monocrystalline PTHZ of 2.0mm x2.0mm x2.0mm size after 10 days with the cuvette substance transfer.
Experiment records: 175.5-176.5 ℃ of PTHZ crystalline melting point of the present invention, as shown in Figure 1, be better than POA-II and POM, the same order of magnitude of 1064nm laser freuqency doubling effect and POA-II and POM, specific refractory power and POA-II are close, be better than POM, uv-visible absorption spectra is measured and is shown maximum absorption band at 223nm as shown in Figure 3, and transparency range is more than the 350-800nm.
The present invention introduces propionyl to improve its physical strength and thermostability (fusing point) at N-(2-thenoyl) hydrazine.N of the present invention, the fusing point of N '-propionyl-(2-thenoyl) hydrazine crystal is high, reaches 175.5-176.5 ℃, and can be used for wavelength is that the laser of 1064nm is converted to 532nm.
Although more than described the specific embodiment of the present invention; but being familiar with those skilled in the art is to be understood that; our described specific embodiment is illustrative; rather than for the restriction to scope of the present invention; those of ordinary skill in the art are in modification and the variation of the equivalence of doing according to spirit of the present invention, all should be encompassed in the scope that claim of the present invention protects.
Claims (4)
1. two-order nonlinear laser material N, N '-propionyl-(2-thenoyl) hydrazine crystal is characterized in that: described N, N '-propionyl-(2-thenoyl) hydrazine crystal belongs to rhombic system, and spacer is P2
12
12
1, molecular formula C
8H
10N
2O
2S, Mr=1988.24, crystallographic parameter:
Z=4, N, N '-propionyl-(2-thenoyl) hydrazine molecule is made of the gentle propionyl of vertical each other N-(2-thenoyl) diazanyl plane.
2. two-order nonlinear laser material N as claimed in claim 1, the growth method of N '-propionyl-(2-thenoyl) hydrazine, it is characterized in that: described method is as follows:
Introduce propionyl at N-(2-thenoyl) hydrazine; then with the N that generates; the isomer of N '-propionyl-(2-thenoyl) hydrazine is dissolved in the imitative pure mixed solvent; and chloroform in the described imitative pure mixed solvent: methyl alcohol=1: 1; and under room temperature, be evaporated to saturated; take out saturated N; the ppolymorphism liquid solution of N '-propionyl-(2-thenoyl) hydrazine places cuvette; apply the volts DS of 36V in the cuvette outside; evaporation grows seed crystal, then seed crystal is transferred to culture tank; same imitative pure mixed solvent evaporation obtains styloid N, N '-propionyl-(2-thenoyl) hydrazine.
3. two-order nonlinear laser material N as claimed in claim 2, the growth method of N '-propionyl-(2-thenoyl) hydrazine is characterized in that: described N, and the isomer crystal of N '-propionyl-(2-thenoyl) hydrazine belongs to triclinic(crystalline)system, spacer is P-1, molecular formula C
8H
10N
2O
2S, Mr=1988.24, crystallographic parameter:
α=70.00 °, β=88.58 °, γ=71.11 °,
Z=6 is without the second order frequency-doubled effect.
4. two-order nonlinear laser material N as claimed in claim 1, the purposes of N '-propionyl-(2-thenoyl) hydrazine crystal is characterized in that: it is that the laser of 1064nm is converted to 532nm that this crystal is used for wavelength.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0850312A (en) * | 1994-08-08 | 1996-02-20 | Toray Ind Inc | Production of organic nonlinear optical crystal |
| CN101071248A (en) * | 2007-04-29 | 2007-11-14 | 华侨大学 | Two-order nonlinear laser material 4-nitro-N-oxy-2-pyridine carboxylic acid second-generation crystal, and its growth method and use |
| CN101984152A (en) * | 2010-11-22 | 2011-03-09 | 中国科学院新疆理化技术研究所 | Nonlinear optical crystal of dimalic acid ammonium borate monohydrate compound and growing method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0850312A (en) * | 1994-08-08 | 1996-02-20 | Toray Ind Inc | Production of organic nonlinear optical crystal |
| CN101071248A (en) * | 2007-04-29 | 2007-11-14 | 华侨大学 | Two-order nonlinear laser material 4-nitro-N-oxy-2-pyridine carboxylic acid second-generation crystal, and its growth method and use |
| CN101984152A (en) * | 2010-11-22 | 2011-03-09 | 中国科学院新疆理化技术研究所 | Nonlinear optical crystal of dimalic acid ammonium borate monohydrate compound and growing method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘国祥: "噻吩酰肼衍生物及其配合物的合成、晶体结构与非线性光学性质研究", 《中国优秀硕士论文全文数据库》 * |
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