WO2017005081A1

WO2017005081A1 - BaHgSe2 NONLINEAR OPTICAL CRYSTAL, PREPARATION METHOD THEREFOR, AND APPLICATION THEREOF

Info

Publication number: WO2017005081A1
Application number: PCT/CN2016/085700
Authority: WO
Inventors: 姚吉勇; 李超; 李小双; 周墨林; 张国春; 吴以成
Original assignee: 中国科学院理化技术研究所
Priority date: 2015-07-07
Filing date: 2016-06-14
Publication date: 2017-01-12
Also published as: CN105113005A; CN105113005B

Abstract

A BaHgSe₂ nonlinear optical crystal has no symmetric center, belongs to the orthorhombic crystal system, and has a space group of Pmc2₁. The crystal cell parameters of the BaHgSe₂ nonlinear optical crystal are: a=4.36 Å, b=14.88 Å, c=7.59 Å, α=β=γ=90°, and Z=4. The preparation method uses the high-temperature melt spontaneous crystallization method or the Bridgman-Stockbarge method for growth. In the growth of the BaHgSe₂ nonlinear optical crystal, the crystal has the advantages of relatively fast growth speed, low cost, easy to obtain a crystal having a relatively large size, and the like. The obtained BaHgSe₂ nonlinear optical crystal has the advantages of large nonlinear optical effect, wide euphotic waveband, high hardness, good mechanical properties, easy to be processed, and the like. The BaHgSe₂ nonlinear optical crystal can be used for preparing a nonlinear optical element. The element comprises an apparatus for generating, after an incoming electromagnetic radiation passes through at least one of the BaHgSe₂ nonlinear optical crystals, an output radiation whose frequency is different from the incoming electromagnetic radiation.

Description

BaHgSe2 nonlinear optical crystal, preparation method and use thereof

Technical field

The present invention relates to the use of _nonlinear optical crystal BaHgSe ₍₂ BaHgSe single crystal) and the method of Preparation ₂ BaHgSe nonlinear optical crystal and the _second nonlinear optical crystal BaHgSe for fabricating nonlinear optical devices.

Background technique

A crystal with a nonlinear optical effect is called a nonlinear optical crystal. Here, the nonlinear optical effect refers to the effects of frequency doubling, sum frequency, difference frequency, and parametric amplification. Only crystals that do not have a center of symmetry may have nonlinear optical effects. By using the nonlinear optical effect of the crystal, nonlinear optical devices such as second harmonic generators, upper and lower frequency converters, and optical parametric oscillators can be fabricated. The laser generated by the laser can be frequency-converted by nonlinear optics to obtain more useful wavelength lasers, making the laser more widely used. According to the different application bands of materials, it can be divided into three categories: ultraviolet light region, visible and near-infrared light region, and medium-infrared light region nonlinear optical material. The nonlinear optical crystal materials in the visible light region and the ultraviolet light region can meet the requirements of practical applications; for example, in the double frequency (532 nm) crystal, KTP (KTiOPO ₄ ), BBO (β-SnB ₂ O ₄ ), LBO (LiB ₃ O ₅ ) crystal; BBO, LBO, CBO (CsB ₃ O ₅ ) are available for selection in triple frequency (355 nm) crystals. The nonlinear crystals in the infrared band develop relatively slowly; the materials in the infrared region are mostly ABC ₂ type chalcopyrite structural semiconductor materials, such as AgGaQ ₂ (Q=S, Se, Te), the optical damage threshold of infrared nonlinear crystals. Too low and crystal growth are difficult, directly affecting the actual use. The mid-infrared nonlinear optical crystal has important applications in the field of optoelectronics. For example, it can extend the near-infrared laser (such as 1.064 μm) to the mid-infrared region by means of optical parametric oscillation or optical parametric amplification; The region's important lasers (such as CO ₂ laser, 10.6 μm) are multiplied, which is important for obtaining lasers with continuously adjustable wavelengths. Therefore, the search for new infrared nonlinear optical crystal materials with excellent performance has become one of the difficult and frontier directions in the research field of nonlinear optical materials.

Summary of the invention

It is an object of the present invention to provide a BaHgSe ₂ nonlinear optical crystal.

Another object of the present invention is to provide a method for preparing a BaHgSe ₂ nonlinear optical crystal.

A further object of the invention is to provide the use of a BaHgSe ₂ nonlinear optical crystal.

The technical solution of the present invention is as follows:

The BaHgSe ₂ nonlinear optical crystal provided by the invention does not have a symmetry center, belongs to an orthorhombic system, and the space group is Pmc2 ₁ , and the unit cell parameters are:

α = β = γ = 90°, Z = 4.

The method for preparing the BaHgSe ₂ nonlinear optical crystal provided by the invention is a high-temperature melt spontaneous crystallization method for growing a BaHgSe ₂ nonlinear optical crystal, the step of: heating a powdery BaHgSe ₂ compound to melt to obtain a melt and maintaining After 24-96 hours, the temperature is lowered to room temperature at a temperature decreasing rate of 1-10 ° C / hour to obtain a BaHgSe ₂ nonlinear optical crystal; or

The Hg source material, the Ba source material, and the elemental Se are uniformly mixed in a molar ratio Ba:Hg:Se=1:1:2, and then melted to obtain a melt for 24-96 hours, and then at 1-10 ° C/ The hourly cooling rate is cooled to room temperature to obtain a BaHgSe ₂ nonlinear optical crystal;

The powdery BaHgSe ₂ compound is prepared by mixing the Hg source material, the Ba source material and the elemental Se in a molar ratio of Ba:Hg:Se=1:1:2, and heating to 800-1150 ° C for solidification. The phase reaction gave a BaHgSe ₂ compound, which was pulverized to obtain a powdery BaHgSe ₂ compound. The Hg source material is Hg or HgSe; and the Ba source material is Ba or BaSe.

The method for preparing a BaHgSe ₂ nonlinear optical crystal provided by the present invention may further grow a BaHgSe ₂ nonlinear optical crystal by a ruthenium lowering method, the steps of which are as follows: the powdery BaHgSe ₂ compound is placed in a crystal growth apparatus, and the temperature is raised to melt, and then , the crystal growth device is vertically lowered at a speed of 0.1-10 mm/h, and BaHgSe ₂ nonlinear optical crystal growth is performed during the falling of the crystal growth device, and the growth period is 5-20 days; or

The Ba source material, the Hg source material and the elemental Se are placed in a crystal growth apparatus at a molar ratio of Ba:Hg:Se=1:1:2, and the temperature is raised until the raw material is melted. After the raw material is completely melted, the crystal growth apparatus is 0.1. -10mm/h speed decreases vertically, BaHgSe ₂ nonlinear optical crystal growth is carried out during the falling of the crystal growth device, and the growth period is 5-20 days;

The powdery BaHgSe ₂ compound is prepared by mixing the Hg source material, the Ba source material and the elemental Se in a molar ratio of Ba:Hg:Se=1:1:2, and heating to 800-1150 ° C for solidification. Phase reaction (in principle, a BaHgSe ₂ compound can be prepared by a general chemical synthesis method; a solid phase reaction method is preferred in the present invention) to obtain a BaHgSe ₂ compound, which is pulverized and ground to obtain a powdery BaHgSe ₂ compound. The Hg source material is Hg or HgSe; and the Ba source material is Ba or BaSe.

According to the crystallographic data of the crystal, the crystal blank is oriented, the crystal is cut according to the desired angle, thickness and section size, and the crystal clear surface is polished to be used as a nonlinear optical device. The BaHgSe ₂ nonlinear optical crystal has nonlinearity. The utility model has the advantages of large optical effect, wide light transmission range, stable physical and chemical properties, large hardness, good mechanical property, not easy to be broken, not easy to deliquesce, easy to process and preserve, etc. Therefore, the present invention further provides the use of BaHgSe ₂ nonlinear optical crystal. The BaHgSe ₂ nonlinear optical crystal is used for preparing a nonlinear optical device, and the prepared nonlinear optical device comprises: generating at least one beam of at least one incident electromagnetic radiation through at least one of the BaHgSe ₂ nonlinear optical crystals to generate at least one beam different from the incident A device for outputting radiation of electromagnetic radiation.

The BaHgSe ₂ nonlinear optical crystal of the present invention and the preparation method and use thereof have the following effects:

In the growth of the BaHgSe ₂ nonlinear optical crystal, the crystal is easy to grow and transparent without encapsulation, and has the advantages of high growth rate, low cost, easy to obtain a large-sized crystal, and the like; the prepared BaHgSe ₂ nonlinear optical crystal has a non- The linear optical effect is large, the light transmission band is wide, the hardness is large, the mechanical properties are good, the cracking and deliquescence are not easy, and the processing and preservation are easy. The BaHgSe ₂ nonlinear optical crystal can be used to fabricate nonlinear optical devices.

DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram showing the operation of a typical nonlinear optical device made of the BaHgSe ₂ nonlinear optical crystal of the present invention, wherein 1 is a laser, 2 is an incident laser beam, and 3 is after crystal post-processing and optical processing. BaHgSe ₂ nonlinear optical crystal, 4 is the generated outgoing laser beam, and 5 is a filter.

2 is a schematic view showing the structure of a BaHgSe ₂ nonlinear optical crystal.

detailed description

Example 1 - Preparation of BaHgSe ₂ Compound

The preparation of the BaHgSe ₂ compound can be carried out optionally by any one of the following chemical reaction formulas, wherein the Hg source material, the Ba source material and the elemental Se are uniformly mixed in a molar ratio of Ba:Hg:Se=1:1:2. Thereafter, the solid phase reaction is carried out by heating to 800-1150 ° C (in principle, the BaHgSe ₂ compound can be prepared by a general chemical synthesis method; the solid phase reaction method is preferred in the present invention), and the BaHgSe ₂ compound can be obtained, and the powder is obtained by crushing and grinding. a BaHgSe ₂ compound; the chemical reaction formula is:

(1) Ba+Hg+2Se=BaHgSe ₂ ;

(2) BaSe+Hg+Se=BaHgSe ₂ ;

(3) Ba+Se+HgSe=BaHgSe ₂ ;

(4) BaSe+HgSe=BaHgSe ₂ .

Example 2 - Preparation of a BaHgSe ₂ nonlinear optical crystal by a high temperature melt spontaneous crystallization method, the specific steps of which are as follows:

Weigh 2.796 g of HgSe and 2.163 g of BaSe (ie, HgSe: BaSe = 0.01 mol: 0.01 mol), uniformly mix, and then put into a quartz glass tube of Φ12 mm×20 mm, evacuate to 10 ^-3 Pa, and use an oxyhydrogen flame. After packaging, it is placed in a tube growth furnace, raised to 1000 ° C, constant temperature for 72 hours, slowly cooled to room temperature at a rate of 1 ° C / h, and the tube growth furnace is turned off; after the quartz tube is cooled and cut, black crystals can be obtained. .

It is of course also possible to directly prepare the BaHgSe ₂ nonlinear optical crystal by the high-temperature melt spontaneous crystallization method using the BaHgSe ₂ compound prepared in Example 1: heating the powdery BaHgSe ₂ compound to melt to obtain a melt and maintaining it for 24-96 hours, to 1 The temperature drop rate of -10 ° C / hour was cooled to room temperature to obtain a BaHgSe ₂ nonlinear optical crystal.

Example 3, the BaHgSe ₂ crystal was prepared by the ruthenium dropping method:

5.591 g of HgSe and 4.326 g of BaSe (Ba:Hg:Se=0.02 mol: 0.02 mol: 0.04 mol) were weighed, uniformly mixed, and then placed in a quartz glass tube of Φ25 mm×200 mm, and evacuated to 10 ^-3 Pa, After being encapsulated with an oxyhydrogen flame, it is placed in a crystal growth furnace, and slowly raised to 1000 ° C to melt the raw material. After the raw material is completely melted, the growth apparatus is vertically lowered at a rate of 0.1-10 mm/hour; after the crystal growth is finished, the growth apparatus is 50. The temperature was lowered to room temperature to obtain a black BaHgSe ₂ crystal.

It is of course also possible to directly prepare the BaHgSe ₂ nonlinear optical crystal by the ruthenium lowering method using the BaHgSe ₂ compound prepared in Example 1: loading the powdery BaHgSe ₂ compound into a quartz glass tube of Φ25 mm×200 mm, and evacuating to 10 ^-3 Pa. After being encapsulated with oxyhydrogen flame, it is placed in a crystal growth furnace, and slowly raised to 1000 ° C to melt the raw material. After the raw material is completely melted, the growth device is vertically lowered at a rate of 0.1-10 mm/hour; after the crystal growth is finished, the growth device is used. The temperature was lowered to room temperature for 50 hours to obtain a black BaHgSe ₂ crystal.

The BaHgSe ₂ nonlinear optical crystal prepared in the above Examples 2-3 was tested to be an orthorhombic system, and the space group was Pmc2 ₁ , and the unit cell parameters were:

α=β=γ=90°, Z=4,

It has a frequency doubling effect, and the light transmission range is 1-20 μm; FIG. 2 is a schematic structural view of the BaHgSe ₂ nonlinear optical crystal.

Example 4:

The BaHgSe ₂ crystal obtained in Example 2-3 is not easily broken, is not easily deliquescent, and is easy to be cut, polished, and preserved. The BaHgSe ₂ crystal obtained in Example 1-2 was placed at the position of the device shown in Fig. 1 at the position of 3, and a Q-switched Ho:Tm:Cr:YAG laser was used as a light source at room temperature, and the incident wavelength was 2090 nm. The infrared light is output at a frequency of 1045 nm, and the laser intensity is equivalent to that of AgGaSe ₂ under the same conditions.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram showing the operation of a typical nonlinear optical device made of the BaHgSe ₂ nonlinear optical crystal of the present invention, wherein 1 is a laser, 2 is an incident laser beam, and 3 is after crystal post-processing and optical processing. BaHgSe ₂ nonlinear optical crystal, 4 is the generated outgoing laser beam, 5 is a filter; the incident laser beam 2 emitted by the laser 1 is incident on the BaHgSe ₂ single crystal 3, and the generated outgoing laser beam 4 passes through the filter 5, and Obtain the desired laser beam.

Devices fabricated using the BaHgSe ₂ nonlinear optical crystal of the present invention may be frequency doubling generators, upper and lower frequency converters, optical parametric oscillators, optical parametric amplifiers, and the like.

Claims

A BaHgSe 2 nonlinear optical crystal having no symmetry center, belonging to an orthorhombic system, and a space group of Pmc2 1 , the unit cell parameters of which are:
α = β = γ = 90°, Z = 4.
A method for preparing a BaHgSe 2 nonlinear optical crystal according to claim 1, which is a high-temperature melt spontaneous crystallization method for growing a BaHgSe 2 nonlinear optical crystal, the step of: heating a powdery BaHgSe 2 compound to melt to obtain a melt After maintaining for 24-96 hours, the temperature is lowered to room temperature at a temperature decreasing rate of 1-10 ° C / hour to obtain a BaHgSe 2 nonlinear optical crystal; or

The Hg source material, the Ba source material, and the elemental Se are uniformly mixed in a molar ratio of Ba:Hg:Se=1:1:2, and then heated to melt to obtain a melt for 24-96 hours, and then at 1-10 ° C. /hour cooling rate is cooled to room temperature to obtain BaHgSe 2 nonlinear optical crystal;

The powdery BaHgSe 2 compound is prepared by mixing the Hg source material, the Ba source material and the elemental Se in a molar ratio of Ba:Hg:Se=1:1:2, and heating to 800-1150 ° C for solidification. The phase reaction gave a BaHgSe 2 compound, which was pulverized to obtain a powdery BaHgSe 2 compound.
The method of preparing a BaHgSe 2 nonlinear optical crystal according to claim 2, wherein the Hg source material is Hg or HgSe; and the Ba source material is Ba or BaSe.
A method for preparing a BaHgSe 2 nonlinear optical crystal according to claim 1, which is a BaHgSe 2 nonlinear optical crystal grown by a ruthenium lowering method, wherein the powder BaHgSe 2 compound is placed in a crystal growth apparatus and heated to melt. Thereafter, the crystal growth apparatus is vertically lowered at a speed of 0.1-10 mm/h, and BaHgSe 2 nonlinear optical crystal growth is performed during the falling of the crystal growth apparatus, and the growth period is 5-20 days; or

The Ba source material, the Hg source material and the elemental Se are placed in a crystal growth apparatus at a molar ratio of Ba:Hg:Se=1:1:2, and the temperature is raised until the raw material is melted. After the raw material is completely melted, the crystal growth apparatus is 0.1. -10mm/h speed decreases vertically, BaHgSe 2 nonlinear optical crystal growth is carried out during the falling of the crystal growth device, and the growth period is 5-20 days;

The powdery BaHgSe 2 compound is prepared by mixing the Hg source material, the Ba source material and the elemental Se in a molar ratio of Ba:Hg:Se=1:1:2, and heating to 800-1150 ° C for solidification. The phase reaction gave a BaHgSe 2 compound, which was pulverized to obtain a powdery BaHgSe 2 compound.
The method of preparing a BaHgSe 2 nonlinear optical crystal according to claim 4, wherein the Hg source material is Hg or HgSe; and the Ba source material is Ba or BaSe.
Use of the BaHgSe 2 nonlinear optical crystal according to claim 1, wherein the BaHgSe 2 nonlinear optical crystal is used for preparing a nonlinear optical device, and the prepared nonlinear optical device comprises at least one incident electromagnetic field Radiation passes through at least one of the BaHgSe 2 nonlinear optical crystals to produce at least one device having a frequency different from the output radiation of the incident electromagnetic radiation.