CN1201082A - Sulfocyanic-acid-matches type crystal material, preparation method and use thereof - Google Patents
Sulfocyanic-acid-matches type crystal material, preparation method and use thereof Download PDFInfo
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- CN1201082A CN1201082A CN 98110133 CN98110133A CN1201082A CN 1201082 A CN1201082 A CN 1201082A CN 98110133 CN98110133 CN 98110133 CN 98110133 A CN98110133 A CN 98110133A CN 1201082 A CN1201082 A CN 1201082A
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Abstract
The present invention relates to a nonlinear optical crystal material and its preparation method and application. In particular, it relates to a sulfocyanic complex type crystal and its growth method and application as non-linear optic material. The chemical formula of said invented material is AB(SCN)4, in which, when A is divalent metals of Ba, Mg, Ca, Mn and Sr, B is divalent metals of Zn, Cd and Hg, etc., and when A is Zn, B is Cd, belonging to tetragonal system, space group is 14. Said invented product possesses good mechanical strength and hardness, high melting point, and can resist cleavage and air-slaking, can be used as non-linear optical frequency converter in laser with bluish violet light output. Said invention uses solution cooling method and evaporation method for crystal growth.
Description
The invention relates to a nonlinear optical material, a preparation method and application thereof, in particular to a thiocyanic acid complex type crystal material, crystal growth and application as a laser frequency conversion device.
Optical functional materials and techniques are the basis and key of modern science and technology. Is also the focus of intense competition in countries of the world. For this reason, it is becoming one of the most rapidly growing areas in the world today. With the major breakthrough and the gradual practicability of the near-infrared semiconductor laser in the eighties. The development of the optoelectronic technology is accelerated towards the miniaturization, high-density and high-speed modern information processing technology, and the storage speed in the information processing technology is proportional to the square of the wavelength of the light source, namely, the shorter the wavelength of the light source is, the larger the storage capacity is. Therefore, the blue-violet light, especially the violet laser material, shows great application value in the fields of optical communication, optical calculation, information storage, modern medicine, life science and the like. The solution of the small, stable and practical blue-violet light source becomes an important development direction in the present photoelectronic field. In the research of direct output of semiconductor laser toward short wavelength, GaN laser diodes developed by japan have been advancing to practical use because they stabilize blue light output for ten thousand hours at room temperature, but it is difficult to realize violet light output at room temperature. Yuandongrong et al reported in 1997 that Cadmium Mercury Thiocyanate (CMTC) crystals were used in physical fast reports (A.P.L.701997544-546) volume 70, page 544 and 546, and a direct frequency doubling near infrared semiconductor laser realized continuous blue-violet light output at milliwatt level at room temperature. The CMTC crystal is AB (SCN)4The crystal has wide light transmission wavelength and large nonlinear coefficient, and is a blue-violet laser frequency doubling material with bright application prospect. However, the ultraviolet cut-off wavelength of the crystal is 380nm, and the transmittance between 380 and 400nm is lower than 50 percent. It is difficult to realize violet laser output of 400nm or less. Light transmission of crystalThe spectral properties are directly linked to the electronic structure of the structural elements of its crystal. By changing AB (SCN)4The material elements can be used for designing and obtaining optical functional materials and devices related to the purple light laser light source which needs to be solved urgently at present.
In order to overcome the disadvantages of the prior art, it is an object of the present invention to provide a novel nonlinear optical material, i.e., a thiocyanate complex-type crystal, of the general formula: is AB (SCN)4。
Another object of the present invention is to provide a process for producing a crystal, which comprises placing a solvent in a vessel, placing the raw materials in a desired ratio to dissolve the raw materials and form a supersaturated solution, then growing the crystal by cooling and/or volatilizing the solvent with or without seed crystals and with or without rotation, cutting the resulting crystal, and polishing and shaping the crystal.
The invention also aims to provide a laser which comprises a laser resonant cavity, a pumping light source and the thiocyanate complex type crystal frequency conversion device.
The chemical general formula of the optical functional crystal material is as follows: AB (SCN)4
Wherein when A is bivalent metal such as Ba, Mg, Ca, Mn, Sr, etc., B is bivalent metal such as Zn, Cd, Hg, etc.
When A is Zn, B is Cd.
Preferred ZnCd (SCN) in the invention4、MgCd(SCN)4、BaCd(SCN)4、MgZn(SCN)4、MnZn(SCN)4、BaZn(SCN)4。
AB(SCN)4The compound belongs to a tetragonal system, space group I4, and the molecular structure is shown in figure 1.
FIG. 1 shows AB (SCN)4Schematic diagram of molecular structure.
FIG. 2 shows AB (SCN)4The structure is schematic.
AB (SCN) of the present invention4The double salt being a complex type non-linearNeutral optical material, A, B as the central metal ion, in generalThen, A coordinates to N to form AN4Teratocarcinolone, the coordination of B and S constituting BS4Distorted tetrahedron, AN4With BN4The electronic bridges N-C-S are connected to form a spatial infinitely extending structural network of the three-dimensional framework. Dipole moment generated by the distorted tetrahedron is transmitted through the electronic bridge, and microscopic dipole moment is mutually superposed in the same direction through the electronic bridge N C S, so that the macroscopic crystal material shows large nonlinear effect. Chemical formula AB (SCN)4The compound (2) is an inorganic/organic complex type optical functional material having high nonlinearity. The crystal has no domain structure, and the application does not need polarization treatment, and the compound has better mechanical strength due to the structural characteristics. The hardness of the KDP crystal is superior to that of the KDP crystal which is widely applied at present, the melting point is higher than that of common organic materials and is more than 200 ℃, deliquescence does not occur at room temperature, and the crystal is not cleaved. The material can be prepared into three-dimensional single crystals and two-dimensional films, and the light-selecting bandwidth and the cut-off wavelength of the material are both less than 400 nm. And the laser can generate frequency conversion through a certain matching mode.
AB (SCN) of the present invention4The compounds can be prepared by the following synthetic methods.
<1>
Prepared AB (SCN)4The yield of the compound is more than 70%.
<2>.
Wherein NH4The SCN can be replaced by NaSCN and KSCN
BCl2、ACl2Available B (NO)3)2，A(NO3)2Or BSO4，
ASO4The substitution yield was above 50%. In the above two methods, the first step,<1>the synthetic method has high yield of the synthesized raw materials, but the steps are complex.<2>The yield is low but the process is simple.
AB (SCN) of the present invention4The single crystal of the complex type optical functional material can be prepared by a solution cooling method, a constant temperature evaporation method and a gel method. The growth conditions are not particularly limited as long as crystals are grown. In general:
the solvent used in the solution cooling method can be organic solvent such as water, methanol, ethanol, isopropanol, etc., and mixed solvent such as ethanol/water, methanol/water, isopropanol/water, KCl/water, dimethyl sulfoxide/water, etc.
The solvent in the constant temperature evaporation method can adopt volatile soluble solvents and mixed solvents such as: water, methanol, ethanol, isopropanol or methanol/water, ethanol/water, isopropanol/water, dimethyl sulfoxide/water.
The appropriate growth method and solvent are chosen for the different compounds. The growth solvent is KCl/water, NaCl/water, NH by solution cooling method4A mixed Cl/water solvent is preferred. The evaporation method is preferably used to dissolve the growth solvent in ethanol/water mixture. Among them, the solution cooling method and the evaporation method are easy to obtain large single crystals with high optical quality.
AB (SCN) of the present invention4The material can be used as a laser frequency conversion device to form a laser with blue-violet light output. The laser conditions are not strictly limited, and any pump light source can be adopted, and generally comprises a condenser, a laser resonant cavity, a pump light source and the thiocyanate complex type crystal frequency doubling device.
The advantageous effects of the present invention have been mentioned in the above summary of the invention, and will be further described below.
The invention is inorganic and organic complex type optical functional material, which has the most application prospect in the range of light-transmitting wave band, and is used for direct frequency doubling of a semiconductor laser to obtain a small blue-violet laser. The small blue-violet laser has a huge market hidden in high-density storage modern medicine, life science and national defense technology. The frequency conversion of the laser can be realized to obtain continuously adjustable green, blue and purple laser.
The inorganic/organic composite complex type nonlinear optical material is a novel composite material which gives consideration to the characteristics of inorganic and organic structural elements. The ZCTC crystal has comprehensive excellent photoelectric properties, and compared with a CMTC which realizes that semiconductor laser frequency doubling generates milliwatt (404-408.5nm) violet light output, the ZCTC crystal has the same-order strong nonlinear optical effect. Further, the transmitted wave was purple shifted by 30 nm. Therefore, the material opens up a new field for the short-wavelength optical functional material.
The invention AB (SCN)4The preparation method is wide and easy, so that the material can be widely applied to high-technology industries such as lasers and the like.
The present invention willbe further described with reference to the following examples. Examples 1-16 are materials of the present invention.
A: 5mm or more, B: more than 3mm, I0: powder double frequency intensity of urea. In the above embodiments, preferred are embodiments 1, 2, 5, 7, 10 and 11.
| Examples | Compound (I) AB(SCN)4 | Crystal | Cut-off wavelength μ | Powder double frequency strength I/I0(150μm) |
| 1 | ZnCd(SCN)4 | A | ＜400 | 10 |
| 2 | MgCd(SCN)4 | A | ＜400 | 10 |
| 3 | CaCd(SCN)4 | A | ＜400 | 10 |
| 4 | SrCd(SCN)4 | B | ＜400 | 10 |
| 5 | BaCd(SCN)4 | A | ＜400 | 10 |
| 6 | MnCd(SCN)4 | B | ＜400 | 9 |
| 7 | MgZn(SCN)4 | A | ＜400 | 7 |
| 8 | CaZn(SCN)4 | A | ＜400 | 10 |
| 9 | SrZn(SCN)4 | B | ＜400 | 10 |
| 10 | MnZn(SCN)4 | B | ＜400 | 10 |
| 11 | BaZn(SCN)4 | A | ＜400 | 7 |
| 12 | MgHg(SCN)4 | B | ＜400 | 10 |
| 13 | BaHg(SCN)4 | B | ＜400 | 10 |
| 14 | CaHg(SCN)4 | B | ＜400 | 10 |
| 15 | MnHg(SCN)4 | A | ＜400 | 7 |
| 16 | SrHg(SCN)4 | B | ＜400 | 10 |
Example 17 growth of ZnCd (SCN) by solution Cooling4Crystal (ZCTC)
Taking dimethyl sulfoxide/water (volume ratio 1: 1) solution as solvent, and performing crystal growth by solution cooling method, wherein the period is 30 days, the crystal size is 3 × 3 × 5(mm), the crystal melting point is 348 deg.C, Mohs hardness is 2.8, and the cut-off wavelength is 350 nm.
EXAMPLE 18 purple light output laser
The method comprises the steps of using the ZCCTC crystal grown in the embodiment 17 as a frequency conversion device, and directly doubling the frequency by using a semiconductor laser with the center wavelength of 809nm to realize the purple light output of 404.5 nm. Compared with the CMTC for outputting purple light, the optical material has the nonlinear optical coefficient with the same order of magnitude, the cutoff wavelength purple shifts by 30nm, the crystal is easy to grow, and the optical material is more suitable for small blue-violet lasers and is potentially huge in application markets in the fields of information storage, modern medical life science and the like.
Claims (10)
1. A nonlinear optical crystal material is characterized in that the chemical formula is as follows: AB (SCN)4Wherein, when A is bivalent metal such as Ba, Mg, Ca, Mn, Sr, etc., B is bivalent metal such as Zn, Cd, Hg, etc.; when A is Zn, B is Cd; belongs to tetragonal system, space group I4.
2. The crystalline material of claim 1, wherein the crystal is ZnCd (SCN)4。
3. The crystalline material of claim 1, wherein the crystal is MgCd (SCN)4。
4. The crystalline material of claim 1, wherein said crystal is bagd (scn)4。
5. The crystalline material of claim 1, wherein the crystal is MgZn (SCN)4。
6. The crystalline material of claim 1, wherein the crystal is MnZn (SCN)4。
7. The crystalline material of claim 1, wherein said crystal is BaZn (SCN)4。
8. A method for preparing the crystal of claim 1, comprising placing a solvent into a container, proportionally placing the raw materials to dissolve and form a supersaturated solution, and cutting and polishing the obtained crystal by cooling and/or volatilizing the solvent under rotation or rotation conditions with or without seed crystal.
9. The method of claim 8, wherein the solvent is reduced in temperature or evaporated.
10. Use of the crystal of claim 1 as a nonlinear optical frequency conversion device for a laser for blue-violet light output.
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| Application Number | Priority Date | Filing Date | Title |
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| CN98110133A CN1062033C (en) | 1998-04-02 | 1998-04-02 | Sulfocyanic-acid-matches type crystal material, preparation method and use thereof |
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| CN98110133A CN1062033C (en) | 1998-04-02 | 1998-04-02 | Sulfocyanic-acid-matches type crystal material, preparation method and use thereof |
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| CN1201082A true CN1201082A (en) | 1998-12-09 |
| CN1062033C CN1062033C (en) | 2001-02-14 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352114C (en) * | 2005-08-16 | 2007-11-28 | 武汉大学 | Application of HgSO4 or CdSO4 as non-linear optical crystal material in optical field |
| CN102660773A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Non-linear optical crystal boric acid cadmium yttrium oxide |
| WO2017005081A1 (en) * | 2015-07-07 | 2017-01-12 | 中国科学院理化技术研究所 | BaHgSe2 NONLINEAR OPTICAL CRYSTAL, PREPARATION METHOD THEREFOR, AND APPLICATION THEREOF |
| CN110499531A (en) * | 2019-09-29 | 2019-11-26 | 中国工程物理研究院化工材料研究所 | A kind of novel bromine barium cyanate birefringece crystal and preparation method thereof |
| CN111485279A (en) * | 2020-05-13 | 2020-08-04 | 中国科学院上海硅酸盐研究所 | Method for preparing lithium molybdate crystal at low temperature by aqueous solution method |
-
1998
- 1998-04-02 CN CN98110133A patent/CN1062033C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352114C (en) * | 2005-08-16 | 2007-11-28 | 武汉大学 | Application of HgSO4 or CdSO4 as non-linear optical crystal material in optical field |
| CN102660773A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院福建物质结构研究所 | Non-linear optical crystal boric acid cadmium yttrium oxide |
| WO2017005081A1 (en) * | 2015-07-07 | 2017-01-12 | 中国科学院理化技术研究所 | BaHgSe2 NONLINEAR OPTICAL CRYSTAL, PREPARATION METHOD THEREFOR, AND APPLICATION THEREOF |
| CN110499531A (en) * | 2019-09-29 | 2019-11-26 | 中国工程物理研究院化工材料研究所 | A kind of novel bromine barium cyanate birefringece crystal and preparation method thereof |
| CN110499531B (en) * | 2019-09-29 | 2020-07-07 | 中国工程物理研究院化工材料研究所 | Barium bromocyanurate birefringent crystal and preparation method thereof |
| CN111485279A (en) * | 2020-05-13 | 2020-08-04 | 中国科学院上海硅酸盐研究所 | Method for preparing lithium molybdate crystal at low temperature by aqueous solution method |
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| Publication number | Publication date |
|---|---|
| CN1062033C (en) | 2001-02-14 |
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