CN107399722A - Selenium silicon silver barium and selenium silicon silver barium mid and far infrared nonlinear optical crystal and preparation method and purposes - Google Patents
Selenium silicon silver barium and selenium silicon silver barium mid and far infrared nonlinear optical crystal and preparation method and purposes Download PDFInfo
- Publication number
- CN107399722A CN107399722A CN201710695513.2A CN201710695513A CN107399722A CN 107399722 A CN107399722 A CN 107399722A CN 201710695513 A CN201710695513 A CN 201710695513A CN 107399722 A CN107399722 A CN 107399722A
- Authority
- CN
- China
- Prior art keywords
- barium
- silicon silver
- nonlinear optical
- selenium
- mid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Glass Compositions (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention relates to a kind of compound selenium silicon silver barium and selenium silicon silver barium mid and far infrared nonlinear optical crystal and preparation method and purposes, its chemical formula is BaAg2SiSe4, molecular weight 697.01, the crystal is tetragonal crystal system, and space group is non-centrosymmetry space group, cell parameter isa=b=7.066 (3),c=8.233 (7),α=β=γ=90°、Z=2, unit-cell volume V=411.1 (5)3；The preparation method is the solid phase reaction of simple substance barium, elemental silver, elemental silicon and elemental selenium under vacuum；The compound selenium silicon silver barium of the present invention and the powder X-ray RD spectrograms and theoretical calculation of selenium silicon silver barium mid and far infrared nonlinear optical crystal；Under 2090 nm laser irradiation, granularity is 55 88μM BaAg2SiSe4Frequency-doubled effect is S-Ga-Ag under equal granularity（AgGaS2）2 times.
Description
Technical field
The invention belongs to infrared nonlinear optical crystal material field, and in particular in a kind of selenium silicon silver barium and selenium silicon silver barium
Far infrared nonlinear optical crystal and preparation method and purposes.
Background technology
Laser as the coherent monochromatic source of a kind of high intensity, good directionality be widely used in scientific research, industry, traffic,
The association area such as national defence and health care.But the laser wavelength that current various lasers directly export is limited, from ultraviolet waves
Section has remained laser blank wave band to infrared band.Due to the particularity of laser genesis mechanism, it is impossible to be each wavelength
Search out a kind of practical laser medium.So frequency conversion is carried out using nonlinear optical crystal to obtain the various laser of broad tuning
Light source has turned into the advanced subject of Development of Laser Technology.
Interaction of the nonlinear optical effect originating from laser and medium.When laser is with non-zero second order susceptibility
During Propagation, the nonlinear optical effect such as frequency multiplication and frequency, difference frequency, optically erasing can be produced.Nonlinear optical crystal material
Material, three major types can be classified as according to its scope through wave band：First, infrared and mid and far infrared nonlinear optical material；2nd, may be used
See light and near infrared band nonlinear optical material；3rd, ultraviolet and deep ultraviolet band nonlinear optical material.Main at present is non-
Linear optical material has：KDP(KH2PO4)、BBO(β-BaB2O4)、LBO(LiB3O5)、AGS(AgGaS2) etc., but due to various originals
Cause, not yet obtain the applicable various nonlinear optical crystals of each wave band.The work of the present invention belongs to visible ray and mid and far infrared
Nonlinear optical material.The non-linear optical crystal material tool of the wave band has been widely used, such as in preparation laser guidance, infrared
Application in the devices such as remote sensor, environmental monitor and coherent infrared radar
Core devices of the infrared nonlinear optical crystal as laser frequency switch technology, it is to utilize the realization pair of non-colinear position technology
Laser frequency conversion is so as to exporting a kind of monocrystal material of tunable mid and far infrared laser.Due to two important atmospheric windows
（3-5μM and 8-14μm）In this wavelength band, therefore explore at present and develop infrared nonlinear optical crystal
It is typically necessary and ensures that there is high transmission ability in the two wavelength bands.
Practical FTIR radiation transmittance is ABC mostly now2The chalcopyrite class of type, such as AgGaS2And ZnGeP2Deng
Commercialized crystal.But the crystalloid has some serious deficiencies, wherein relatively low laser damage threshold, swashing to near-infrared
Light（Such as Nd:YAG 1064 nm）Two-photon absorption problem, serious anisotropic thermal expansion causes to be difficult to obtain large scale height
Quality single crystalline etc., all seriously limit their practical application.
At present in the world, although some the oxide nonlinear optical crystals found solve near-infrared well
Frequency conversion problem, but for 3-5μThe laser of m scopes, lattice vibration frequency and the wave band of many oxide crystals
Laser frequency is suitable, so as to cause the strong competition of radiationless relaxation and Laser emission, can cause the high passive loss of laser, very
Hardly possible output 4μMore than m mid and far infrared laser.Therefore effective mid and far infrared nonlinear optical crystal is explored at present mainly to concentrate
In halide, sulfide or phosphide of non-oxygen system etc..
The content of the invention
First purpose of the present invention, there is provided a kind of compound selenium silicon silver barium, the chemical formula of the compound are
BaAg2SiSe4, molecular weight 697.01, it is non-centrosymmetric structure monocrystalline, belongs to tetragonal crystal system, space group is, it is brilliant
Born of the same parents' parameter isa = b =7.066 (3),c =8.233 (7),α= β= γ= 90°、Z =2, unit-cell volume V=
411.1(5) Å3, polycrystal powder is made using solid reaction process；
Second object of the present invention, there is provided a kind of selenium silicon silver barium mid and far infrared nonlinear optical crystal and preparation method, the crystalline substance
Body chemical formula is BaAg2SiSe4, molecular weight 697.01, it is non-centrosymmetric structure monocrystalline, belongs to tetragonal crystal system, space group is, cell parameter isa = b =7.066 (3),c =8.233 (7),α= β= γ= 90°、Z =2, unit cell body
Product V=411.1 (5)3.The preparation method is the solid phase of simple substance barium, elemental silver, elemental silicon and elemental selenium under vacuum
Reaction；The compound selenium silicon silver barium of the present invention and the powder X-ray RD spectrograms of selenium silicon silver barium mid and far infrared nonlinear optical crystal and reason
It is coincide by value；Under 2090 nm laser irradiation, granularity 55-88μM BaAg2SiSe4Frequency-doubled effect is equal particle
The lower S-Ga-Ag of degree（AgGaS2）2 times.
The 3rd purpose of the present invention provide selenium silicon silver barium mid and far infrared nonlinear optical crystal prepare infrared communication device,
Purposes in infrared band laser frequency-doubling crystal and infrared laser guidance device.
A kind of compound selenium silicon silver barium of the present invention, it is characterised in that the chemical formula of the compound is BaAg2SiSe4,
Molecular weight is 697.01, belongs to tetragonal crystal system, and space group is, cell parameter isa = b =7.066 (3),c =
8.233 (7),α= β= γ= 90°、Z =2, unit-cell volume V=411.1 (5)3, it is polycrystal powder.
The preparation method of described compound selenium silicon silver barium, using high-temperature solid phase reaction method, concrete operations follow these steps
Carry out：
A, it is in the glove box filled with inert nitrogen gas in the gas-tight container that water content and oxygen content are 0.01-0.1 ppm
By Ba:Ag:Si:Se mol ratios 1:2:1:4 it is well mixed after be put into clean graphite crucible, load a length of 20 cm, a diameter of
In 10 mm quartz glass tube, by the quartz ampoule equipped with raw material vacuum be 10-5-10-3Sealed after being vacuumized under conditions of Pa
Mouthful；
B, the quartz ampoule sealed in step a is risen to 400-700 DEG C with 20-40 DEG C/h of temperature heating rate from room temperature, insulation
30-60 hours, then 800-1050 DEG C is warming up to 20-40 DEG C/h of temperature, it is incubated 70-110 hours；
C, room temperature is cooled down to 2-7 DEG C/h of temperature speed, taking-up sample, which is put into mortar, to be smashed to pieces, is ground, that is, is obtained chemical combination
Thing BaAg2SiSe4Polycrystal powder, obtained compound selenium silicon silver barium polycrystal powder is subjected to X-ray analysis, gained X-ray diffraction
Spectrogram and the BaAg parsed with mono-crystalline structures2SiSe4Theoretical X-ray spectrogram is consistent.
A kind of selenium silicon silver barium mid and far infrared nonlinear optical crystal, the crystal-chemical formula are BaAg2SiSe4, molecular weight is
697.01, it is non-centrosymmetric structure monocrystalline, belongs to tetragonal crystal system, space group is, cell parameter isa = b =
7.066 (3),c =8.233 (7),α= β= γ= 90°、Z =2, unit-cell volume V=411.1 (5)3。
The preparation method of described selenium silicon silver barium mid and far infrared nonlinear optical crystal, follows these steps to carry out：
A, it is in the glove box filled with inert nitrogen gas in the gas-tight container that water content and oxygen content are 0.01-0.1 ppm
By by Ba:Ag:Si:Se mol ratios 1:2:1:4 it is well mixed after be put into clean graphite crucible, load a length of 20 cm, diameter
In quartz glass tube for 10 mm, by the quartz ampoule equipped with raw material vacuum be 10-5-10-3After being vacuumized under conditions of Pa
Sealing；
B, the quartz ampoule sealed in step a is risen to 400-700 DEG C from room temperature with 20-40 DEG C/h of temperature heating rate, protected
Warm 30-60 hours, then 800-1050 DEG C is warming up to 20-40 DEG C/h of temperature, it is incubated 70-110 hours；
C, room temperature is cooled down to 2-7 DEG C/h of temperature speed, obtains selenium silicon silver barium BaAg2SiSe4Mid and far infrared nonlinear optical
Learn crystal.
The selenium silicon silver barium mid and far infrared nonlinear optical crystal is preparing infrared communication device, infrared band laser frequency multiplication
Purposes in crystal and infrared laser guidance device.
The powder xrd pattern of selenium silicon silver barium and selenium silicon silver barium mid and far infrared nonlinear optical crystal of the present invention is kissed with theoretical value
Close；Under 2090 nm laser irradiation, granularity 55-88μM BaAg2SiSe4Frequency-doubled effect is sulphur under equal granularity
Gallium silver（AgGaS2）2 times.
In selenium silicon silver crystal of barium structure of the present invention, Ba atoms, Ag atoms, Si atoms, the chemical valence difference of Se atoms
For+2 ,+1 ,+4, -2；Si atoms form isolated existing [SiSe with neighbouring four Se atoms4] tetrahedral structure；Ag atoms
Four adjacent Se atoms form [AgSe4] tetrahedron, and layer structure, layer and layer are formed with the connected mode on common summit
Between by isolated [SiSe4] tetrahedron connects to form [Ag2Si2] quaternary annulus；Ba atoms are then only embedded in [AgSe4]
Tetrahedron and [SiSe4] in the quaternary annulus that is formed of tetrahedron, form [the BaSe of 8 coordinations8] polyhedron；All originals
Son, it is interconnected to form tridimensional network.
Selenium silicon silver barium and selenium silicon silver barium mid and far infrared nonlinear optical crystal of the present invention and preparation method and purposes,
Using the method for high temperature process heat, it is non-linear a kind of compound selenium silicon silver barium and selenium silicon silver barium mid and far infrared has successfully been synthesized
Optical crystal.With the selenium copper silicon barium of number of patent application 201710388528.4 and selenium copper silicon barium mid and far infrared nonlinear optical crystal and
Preparation method compares with purposes, and the crystallographic system belonging to it is by trigonal system（BaCu2SiSe4）It is converted to tetragonal crystal system
（BaAg2SiSe4）, by tridimensional network from structure（BaCu2SiSe4）It is changed into layer structure（BaAg2SiSe4）；
This just illustrates that the two compounds are not only that a simple element isomorphism substitutes, but there occurs the transformation in structure, and
Transformation in this structure causes selenium silicon silver crystal of barium to have more excellent optical property：（1）Use ultraviolet-visible-near-infrared
The spectrometer that diffuses have evaluated the band gap of selenium silicon silver crystal of barium, and as a result show has compared to selenium copper silicon crystal of barium, the compound
Bigger band gap；（2）Its powder laser damage threshold is tested using the method for irradiating powder sample under 1064 nm laser
Value, the results showed that selenium silicon silver crystal of barium powder has bigger laser damage threshold；（3）Measured using the method for powder frequency doubling
The nonlinear response intensity of selenium silicon silver barium, the results showed that it can realize Ho:Tm:Cr:YAG (2090 nm) 2 frequencys multiplication, and its
Powder SHG effect is AgGaS under equal granularity22 times of crystal, show that selenium silicon silver crystal of barium has stronger nonlinear optical
Learn effect.The optical property excellent above that selenium silicon silver crystal of barium has, makes it have bigger potential using value.
Selenium silicon silver barium compound of the present invention is selenium silicon silver barium polycrystal powder.
Brief description of the drawings
Fig. 1 is the comparison diagram of polycrystal powder X-ray powder diffraction figure of the present invention and theoretical value, and wherein A is theoretical value, and B is
Experiment value；
Fig. 2 is BaAg of the present invention2SiSe4The structure chart of crystal；
Fig. 3 be selenium silicon silver barium mid and far infrared nonlinear optical crystal of the present invention under 2090 nm laser, granularity 55-88μm
When and with granularity S-Ga-Ag frequency multiplication comparison diagram, wherein A is AgGaS2Secondary frequency multiplication effect figure, B are BaAg2SiSe4Secondary frequency multiplication
Effect figure；
Fig. 4 is frequency-doubled effect schematic diagram of the present invention.
Embodiment
The present invention is described in detail by embodiment, but is not limited only to given embodiment.
Embodiment 1
The preparation of compound selenium silicon silver barium polycrystal powder：
A, it is in the glove box filled with inert nitrogen gas in the gas-tight container that water content and oxygen content are 0.01-0.1 ppm
By simple substance Ba, simple substance Ag, simple substance Si and simple substance Se in molar ratio 1:2:1:4 it is well mixed after be put into clean graphite crucible,
Be fitted into a length of 20 cm, a diameter of 10 mm quartz glass tube, by the quartz ampoule equipped with raw material vacuum be 10-5-10-3
Sealed after being vacuumized under conditions of Pa；
B, the quartz ampoule sealed in step a is risen to 400-700 DEG C from room temperature with 20-40 DEG C/h of temperature heating rate, protected
Warm 30-60 hours, then 800-1050 DEG C is warming up to 20-40 DEG C/h of temperature, 70-110 hours are incubated, obtain compound；
C, the compound for obtaining step b cools down to room temperature with 2-7 DEG C/h of temperature speed, takes out sample and is put into mortar
Smash to pieces, grind, that is, obtain kermesinus compound BaAg2SiSe4Polycrystal powder, the compound selenium silicon silver barium polycrystal powder that will be obtained
Carry out X-ray analysis, gained X-ray diffraction spectrogram and the BaAg parsed with mono-crystalline structures2SiSe4Theoretical X-ray spectrogram is consistent,
As a result referring to Fig. 1, as seen from the figure, experiment value matches with theoretical value, and the powder sample for illustrating to obtain is pure phase.
Embodiment 2
The preparation of selenium silicon silver barium mid and far infrared nonlinear optical crystal：
A, it is by Ba in the glove box filled with inert nitrogen gas in the gas-tight container that water content and oxygen content are 0.01 ppm:
Ag:Si:Se mol ratios 1:2:1:4 it is well mixed after be put into clean graphite crucible, load a length of 20 cm, a diameter of 10 mm
Quartz glass tube in, by the quartz ampoule equipped with raw material vacuum be 10-5-10-3Sealed after being vacuumized under conditions of Pa；
B, the quartz ampoule sealed in step a is risen to 400 DEG C with 20 DEG C/h of temperature heating rate from room temperature, insulation 30 is small
When, then 800 DEG C are warming up to 20 DEG C/h of temperature, it is incubated 70 hours；
C, room temperature is cooled down to 2 DEG C/h of temperature speed, takes out graphite crucible, obtain kermesinus bulk selenium silicon silver barium
BaAg2SiSe4Mid and far infrared nonlinear optical crystal, by single-crystal X-ray diffraction analysis, it is in selenium silicon silver barium to show the crystal
Far infrared nonlinear optical crystal.
Embodiment 3
The preparation of selenium silicon silver barium mid and far infrared nonlinear optical crystal：
A, being in the gas-tight container that water content and oxygen content are 0.05 ppm will be single in the glove box filled with inert nitrogen gas
Matter Ba, simple substance Ag, simple substance Si and simple substance Se in molar ratio 1:2:1:4 it is well mixed after be put into clean graphite crucible, load
A length of 20 cm, a diameter of 10 mm quartz glass tube in, by the quartz ampoule equipped with raw material vacuum be 10-5-10-3Pa's
Under the conditions of vacuumize after seal；
B, the quartz ampoule sealed in step a is risen to 600 DEG C with 40 DEG C/h of temperature heating rate from room temperature, insulation 50 is small
When, then 1000 DEG C are warming up to 30 DEG C/h of temperature, it is incubated 100 hours；
C, room temperature is cooled down to 4 DEG C/h of temperature speed, takes out graphite crucible, obtain kermesinus bulk selenium silicon silver barium
BaAg2SiSe4Mid and far infrared nonlinear optical crystal.
Embodiment 4
The preparation of selenium silicon silver barium mid and far infrared nonlinear optical crystal：
A, it is by Ba in the glove box filled with inert nitrogen gas in the gas-tight container that water content and oxygen content are 0.08 ppm:
Ag:Si:Se mol ratios 1:2:1:4 it is well mixed after be put into clean graphite crucible, load a length of 20 cm, a diameter of 10 mm
Quartz glass tube in, by the quartz ampoule equipped with raw material vacuum be 10-5-10-3Sealed after being vacuumized under conditions of Pa；
B, the quartz ampoule sealed in step a is risen to 700 DEG C with 38 DEG C/h of temperature heating rate from room temperature, insulation 60 is small
When, then 1050 DEG C are warming up to 40 DEG C/h of temperature, it is incubated 110 hours；
C, room temperature is cooled down to 7 DEG C/h of temperature speed, takes out graphite crucible, obtain kermesinus bulk selenium silicon silver barium
BaAg2SiSe4Mid and far infrared nonlinear optical crystal.
Embodiment 5
The preparation of selenium silicon silver barium mid and far infrared nonlinear optical crystal：
A, it is by simple substance in the glove box filled with inert nitrogen gas in the gas-tight container that water content and oxygen content are 0.1 ppm
Ba, simple substance Ag, simple substance Si and simple substance Se in molar ratio 1:2:1:4 it is well mixed after be put into clean graphite crucible, load length
For 20 cm, a diameter of 10 mm quartz glass tube in, by the quartz ampoule equipped with raw material vacuum be 10-5-10-3Pa bar
Sealed after being vacuumized under part；
B, the quartz ampoule sealed in step a is risen to 500 DEG C with 35 DEG C/h of temperature heating rate from room temperature, insulation 45 is small
When, then 950 DEG C are warming up to 35 DEG C/h of temperature, it is incubated 95 hours；
C, room temperature is cooled down to 5 DEG C/h of temperature speed, takes out graphite crucible, obtain kermesinus bulk selenium silicon silver barium
BaAg2SiSe4Mid and far infrared nonlinear optical crystal.
Embodiment 6
By any one selenium silicon silver barium mid and far infrared nonlinear optical crystal of gained in embodiment 2-5, disposed by accompanying drawing 4 Suo Shi
On 3 position, at room temperature, with tune Q Ho:Tm:Cr:Light source is made in the 2090 nm outputs of YAG laser, it was observed that significantly
1045 nm frequency multiplication light outputs, the intensity of output and AgGaS under the conditions of equal granularity2Equal (as shown in Figure 3).By adjusting Q
Ho:Tm:Cr:YAG laser 1 sends the infrared beam that wavelength is 2090 nm and injects selenium silicon silver barium nonlinear optical through convex lens 2
Crystal is learned, produces the frequency doubled light that wavelength is 1045 nm, outgoing beam 4 contains the infrared light and 1045 nm that wavelength is 2090 nm
Light, filtered 5 filter off after obtain wavelength be 1045 nm frequency doubled light.
Claims (5)
1. a kind of compound selenium silicon silver barium, it is characterised in that the chemical formula of the compound is BaAg2SiSe4, molecular weight is
697.01, belong to tetragonal crystal system, space group is, cell parameter isa = b =7.066 (3),c = 8.233(7)
,α= β = γ = 90°、Z =2, unit-cell volume V=411.1 (5)3, it is polycrystal powder.
2. the preparation method of compound selenium silicon silver barium according to claim 1, it is characterised in that using high temperature solid state reaction
Method, concrete operations follow these steps to carry out：
A, it is in the glove box filled with inert nitrogen gas in the gas-tight container that water content and oxygen content are 0.01-0.1 ppm
By Ba:Ag:Si:Se mol ratios 1:2:1:4 it is well mixed after be put into clean graphite crucible, load a length of 20 cm, a diameter of
In 10 mm quartz glass tube, by the quartz ampoule equipped with raw material vacuum be 10-5-10-3Sealed after being vacuumized under conditions of Pa
Mouthful；
B, the quartz ampoule sealed in step a is risen to 400-700 DEG C with 20-40 DEG C/h of temperature heating rate from room temperature, insulation
30-60 hours, then 800-1050 DEG C is warming up to 20-40 DEG C/h of temperature, it is incubated 70-110 hours；
C, room temperature is cooled down to 2-7 DEG C/h of temperature speed, taking-up sample, which is put into mortar, to be smashed to pieces, is ground, that is, is obtained chemical combination
Thing BaAg2SiSe4Polycrystal powder, obtained compound selenium silicon silver barium polycrystal powder is subjected to X-ray analysis, gained X-ray diffraction
Spectrogram and the BaAg parsed with mono-crystalline structures2SiSe4Theoretical X-ray spectrogram is consistent.
3. a kind of selenium silicon silver barium mid and far infrared nonlinear optical crystal, it is characterised in that the crystal-chemical formula is BaAg2SiSe4, point
Son amount is 697.01, is non-centrosymmetric structure monocrystalline, belongs to tetragonal crystal system, space group is, cell parameter isa = b
=7.066 (3),c =8.233 (7),α= β = γ = 90°、Z =2, unit-cell volume V=411.1 (5)3。
4. the preparation method of selenium silicon silver barium mid and far infrared nonlinear optical crystal as claimed in claim 3, it is characterised in that press
The following steps are carried out：
A, it is in the glove box filled with inert nitrogen gas in the gas-tight container that water content and oxygen content are 0.01-0.1 ppm
By by Ba:Ag:Si:Se mol ratios 1:2:1:4 it is well mixed after be put into clean graphite crucible, load a length of 20 cm, diameter
In quartz glass tube for 10 mm, by the quartz ampoule equipped with raw material vacuum be 10-5-10-3After being vacuumized under conditions of Pa
Sealing；
B, the quartz ampoule sealed in step a is risen to 400-700 DEG C from room temperature with 20-40 DEG C/h of temperature heating rate, protected
Warm 30-60 hours, then 800-1050 DEG C is warming up to 20-40 DEG C/h of temperature, it is incubated 70-110 hours；
C, room temperature is cooled down to 2-7 DEG C/h of temperature speed, obtains selenium silicon silver barium BaAg2SiSe4Mid and far infrared nonlinear optical
Learn crystal.
5. selenium silicon silver barium mid and far infrared nonlinear optical crystal as claimed in claim 3 is preparing infrared communication device, infrared
Purposes in wave band of laser frequency-doubling crystal and infrared laser guidance device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710695513.2A CN107399722B (en) | 2017-08-15 | 2017-08-15 | Selenium silicon silver barium and selenium silicon silver barium mid and far infrared nonlinear optical crystal and preparation method and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710695513.2A CN107399722B (en) | 2017-08-15 | 2017-08-15 | Selenium silicon silver barium and selenium silicon silver barium mid and far infrared nonlinear optical crystal and preparation method and purposes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107399722A true CN107399722A (en) | 2017-11-28 |
| CN107399722B CN107399722B (en) | 2019-05-14 |
Family
ID=60398013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710695513.2A Active CN107399722B (en) | 2017-08-15 | 2017-08-15 | Selenium silicon silver barium and selenium silicon silver barium mid and far infrared nonlinear optical crystal and preparation method and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107399722B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108588840A (en) * | 2018-06-15 | 2018-09-28 | 中国科学院新疆理化技术研究所 | Boron barium sulphide mid and far infrared nonlinear optical crystal and preparation method and application |
| CN110578173A (en) * | 2019-10-25 | 2019-12-17 | 河北大学 | Nonlinear optical crystal strontium-lithium-silicon-sulfur and preparation method and application thereof |
| CN110735184A (en) * | 2018-07-19 | 2020-01-31 | 中国科学院理化技术研究所 | BaHgGeSe seeds4Nonlinear optical crystal and preparation method and application thereof |
| CN111118594A (en) * | 2020-01-16 | 2020-05-08 | 中国科学院上海硅酸盐研究所 | Nonlinear optical crystal material and preparation method and application thereof |
| CN112323145A (en) * | 2020-10-16 | 2021-02-05 | 扬州大学 | Infrared nonlinear optical crystal KAg3Ga8Se14And preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104674349A (en) * | 2015-03-18 | 2015-06-03 | 遵义师范学院 | Infrared nonlinear optical crystal La3Sb0.33SiS7 and preparation method thereof |
| CN104695022A (en) * | 2015-03-09 | 2015-06-10 | 中国科学院合肥物质科学研究院 | Long wave infrared nonlinear CdGa2Se4 crystal as well as growth method and use of crystal |
| CN105603531A (en) * | 2014-11-17 | 2016-05-25 | 中国科学院福建物质结构研究所 | Mid-infrared nonlinear optical crystal, preparation method and applications thereof |
| CN106757365A (en) * | 2016-12-06 | 2017-05-31 | 中国科学院福建物质结构研究所 | A kind of crystalline material, its preparation method and the nonlinear optical crystal comprising it |
| CN106978630A (en) * | 2017-05-27 | 2017-07-25 | 中国科学院新疆理化技术研究所 | Selenium copper silicon barium and selenium copper silicon barium mid and far infrared nonlinear optical crystal and preparation method and purposes |
-
2017
- 2017-08-15 CN CN201710695513.2A patent/CN107399722B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603531A (en) * | 2014-11-17 | 2016-05-25 | 中国科学院福建物质结构研究所 | Mid-infrared nonlinear optical crystal, preparation method and applications thereof |
| CN104695022A (en) * | 2015-03-09 | 2015-06-10 | 中国科学院合肥物质科学研究院 | Long wave infrared nonlinear CdGa2Se4 crystal as well as growth method and use of crystal |
| CN104674349A (en) * | 2015-03-18 | 2015-06-03 | 遵义师范学院 | Infrared nonlinear optical crystal La3Sb0.33SiS7 and preparation method thereof |
| CN106757365A (en) * | 2016-12-06 | 2017-05-31 | 中国科学院福建物质结构研究所 | A kind of crystalline material, its preparation method and the nonlinear optical crystal comprising it |
| CN106978630A (en) * | 2017-05-27 | 2017-07-25 | 中国科学院新疆理化技术研究所 | Selenium copper silicon barium and selenium copper silicon barium mid and far infrared nonlinear optical crystal and preparation method and purposes |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108588840A (en) * | 2018-06-15 | 2018-09-28 | 中国科学院新疆理化技术研究所 | Boron barium sulphide mid and far infrared nonlinear optical crystal and preparation method and application |
| CN108588840B (en) * | 2018-06-15 | 2020-12-11 | 中国科学院新疆理化技术研究所 | Barium borosulfide middle and far infrared nonlinear optical crystal and preparation method and application thereof |
| CN110735184A (en) * | 2018-07-19 | 2020-01-31 | 中国科学院理化技术研究所 | BaHgGeSe seeds4Nonlinear optical crystal and preparation method and application thereof |
| CN110735184B (en) * | 2018-07-19 | 2021-06-08 | 中国科学院理化技术研究所 | BaHgGeSe4Nonlinear optical crystal and preparation method and application thereof |
| CN110578173A (en) * | 2019-10-25 | 2019-12-17 | 河北大学 | Nonlinear optical crystal strontium-lithium-silicon-sulfur and preparation method and application thereof |
| CN111118594A (en) * | 2020-01-16 | 2020-05-08 | 中国科学院上海硅酸盐研究所 | Nonlinear optical crystal material and preparation method and application thereof |
| CN111118594B (en) * | 2020-01-16 | 2021-08-31 | 中国科学院上海硅酸盐研究所 | Nonlinear optical crystal material and preparation method and application thereof |
| CN112323145A (en) * | 2020-10-16 | 2021-02-05 | 扬州大学 | Infrared nonlinear optical crystal KAg3Ga8Se14And preparation method and application thereof |
| CN112323145B (en) * | 2020-10-16 | 2024-02-13 | 扬州大学 | Infrared nonlinear optical crystal KAg 3 Ga 8 Se 14 Method for producing the same and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107399722B (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107399722B (en) | Selenium silicon silver barium and selenium silicon silver barium mid and far infrared nonlinear optical crystal and preparation method and purposes | |
| CN101545141B (en) | Gallium and barium sulfide monocrystal as well as growing method and infrared nonlinear optical device thereof | |
| CN103031607B (en) | Infrared nonlinear optical crystal AB4C5Se12 | |
| CN102976287B (en) | BaGa2GeSe6Compound and BaGa2GeSe6Nonlinear optical crystal and its preparation method and use | |
| Jiang et al. | Large crystal growth and new crystal exploration of mid-infrared second-order nonlinear optical materials | |
| CN102838093B (en) | LiGaGe2Se6Compound, LiGaGe2Se6Nonlinear optical crystal and its preparation method and use | |
| CN116240633A (en) | Compound orthorhombic selenium gallium barium and orthorhombic selenium gallium barium nonlinear optical crystal, preparation method and application thereof | |
| US20170269456A1 (en) | Nonlinear optical crystal material, method for preparation thereof, and application thereof | |
| CN102094245A (en) | Selenium-gallium-aluminum-barium compound, selenium-gallium-aluminum-barium nonlinear optical crystal, preparation method and application | |
| CN103058266A (en) | BaGa2GeS6Compound and BaGa2GeS6Nonlinear optical crystal and its preparation method and use | |
| CN110578173B (en) | Nonlinear optical crystal strontium-lithium-silicon-sulfur and preparation method and application thereof | |
| CN106978630B (en) | Selenium copper silicon barium and selenium copper silicon barium mid and far infrared nonlinear optical crystal and preparation method and purposes | |
| CN107557868A (en) | Sulphur germanium cadmium sodium and sulphur germanium cadmium sodium infrared nonlinear optical crystal and preparation method and application | |
| US11932965B2 (en) | Nonlinear optical crystal, method for preparing the same and application thereof | |
| CN108004596A (en) | Compound sulphur silicon zinc lithium and sulphur silicon zinc lithium infrared nonlinear optical crystal and preparation method and application | |
| CN111593409A (en) | Infrared nonlinear optical chalcogenide LixAg1-xGaS2And preparation method and application thereof | |
| CN103060917A (en) | BaGa2SiS6Compound and BaGa2SiS6Nonlinear optical crystal and its preparation method and use | |
| CN103030146B (en) | BaGa2SiSe6Compound and BaGa2SiSe6Nonlinear optical crystal and its preparation method and use | |
| CN107557867A (en) | Sulphur tin zinc sodium and sulphur tin zinc sodium mid and far infrared nonlinear optical crystal and preparation method and application | |
| CN110079858B (en) | Cesium magnesium sulfate nonlinear optical crystal and preparation method and application thereof | |
| CN104213193A (en) | Phosphomolybdate compound, phosphomolybdate nonlinear optical crystal, preparation method and application | |
| CN106757366A (en) | A kind of crystalline material, its preparation method and the application in nonlinear optical crystal | |
| CN111188092B (en) | Cadmium-zinc-silicon-sulfur crystal and preparation method and application thereof | |
| CN115893478B (en) | Bromine sulfur germanium lead compound and preparation method and application thereof | |
| CN103352252B (en) | Molybdenum potassium nitrate compound, nonlinear optical crystal thereof, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |