CN106629819A - Compound SrCdGeS4 and preparation method thereof, and infrared nonlinear optical crystal as well as preparation method and application thereof - Google Patents
Compound SrCdGeS4 and preparation method thereof, and infrared nonlinear optical crystal as well as preparation method and application thereof Download PDFInfo
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- CN106629819A CN106629819A CN201610898089.7A CN201610898089A CN106629819A CN 106629819 A CN106629819 A CN 106629819A CN 201610898089 A CN201610898089 A CN 201610898089A CN 106629819 A CN106629819 A CN 106629819A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G17/00—Compounds of germanium
- C01G17/006—Compounds containing, besides germanium, two or more other elements, with the exception of oxygen or hydrogen
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- 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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/02—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method without using solvents
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/353—Frequency conversion, i.e. wherein a light beam is generated with frequency components different from those of the incident light beams
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
Abstract
The invention discloses a compound SrCdGeS4 and a preparation method thereof, and an infrared nonlinear optical crystal as well as a preparation method and application thereof. A SrCdGeS4 compound pure phase is prepared by adopting a high-temperature solid-phase reaction method through two times of sintering, and the infrared nonlinear optical crystal grows by adopting a horizontal gradient condensation method or a Bridgman method. According to the method disclosed by the invention, the crystal easily grows and has relatively high quality; and the method the advantages of relatively high growth speed, low cost and easiness of obtaining crystals with relatively large sizes. An infrared nonlinear powder frequency doubling test shows that under the irradiation of fundamental frequency light which is 2090nm laser, the SrCdGeS4 has a very high nonlinear effect; and the frequency doubling signal intensity in a grain diameter range of 41mu m-74mu m is about three times of the signal intensity of an infrared classic material AgGaS2 with the same grain diameter. An infrared nonlinear optical crystal material SrCdGeS4 obtained by the invention has a potential application value in the field of infrared laser frequency conversion.
Description
Technical field
The present invention relates to field of inorganic materials, more particularly it relates to powdered compounds SrCdGeS4And its system
Preparation Method, with powdered compounds SrCdGeS4Obtained infrared nonlinear optical crystal and its preparation method and application.
Background technology
Laser instrument is one of greatest invention of the eighties of last century mankind, is born in nineteen sixty.And with the appearance of laser instrument,
A series of novel optical phenomenas are found that nonlinear optical effect is one of them in succession.1961, Franken
(Franken) in a branch of ruby laser light irradiation to quartz crystal, First Observation is pulled open to nonlinear optics frequency-doubled effect
The prelude of nonlinear optical material research.Through the development of decades, nonlinear optical crystal has been developed as a class and swashs
The important photoelectric functional material that light technology is combined closely.The crystalloid can be shaken by frequency multiplication, difference frequency and frequency and optical parameter
The regulation that second order nonlinear effect is realized to laser frequency such as swing, produce new lasing light emitter, and then greatly expand the application of laser
Scope.
At present, in Uv and visible light wave band, a series of outstanding nonlinear optical crystals are advantageously, it has been found that including KBBF
(KBe2BO3F2)、BBO(β-BaB2O4)、LBO(LiB3O5)、CBO(CsB3O5)、KDP(KH2PO4) and KTP (KTiOPO4) etc., it
Have been obtained for being widely applied and disclosure satisfy that in terms of new Uv and visible light wave band of laser is produced it is various using will
Ask.However, the research to infrared band nonlinear optical crystal is still relatively deficient at present, practical amount of crystals is less simultaneously
Mainly ZGP (the ZnGeP with yellow copper structure2)、AGS(AgGaS2) and AGSe (AgGaSe2).These crystal are present
Serious deficiency, including serious anisotropic thermal expansion causes the preparation of large scale high-quality crystal to be the devil；AGS and
AGSe laser damage thresholds are relatively low to cause laser output power not high；There is serious photonic absorption etc. in ZGP near infrared regions.
These problems significantly limit their practical application.Therefore, find to have and be easy to grow, be machined that property is good, height
Laser damage threshold, the novel crystal of infrared non-linear function admirable seem particularly urgent, are also current nonlinear optical material
One of the study hotspot and difficult point in field.
Chalcogen compound is due to infrared transmittivity is high, infrared transmission wide ranges and nonlinear factor are more excellent than larger etc.
Point, is the main study subject of novel infrared nonlinear optical crystal exploration.For Sr/Cd/Ge/S quaternary chalcogenide objects
System, has no at present research report, and the present invention is the report of the system the first chalcogen compound in terms of FTIR radiation transmittance
Road.
The content of the invention
It is an object of the invention to provide a kind of compound SrCdGeS4And its infrared nonlinear optical crystal, and chemical combination
Thing SrCdGeS4With the respective preparation method of infrared nonlinear optical crystal, the application of infrared nonlinear optical crystal.
In order to achieve the above object, one embodiment of the present invention is employed the following technical solutions：
A kind of compound, its chemical formula is SrCdGeS4。
Compound SrCdGeS4Preparation method comprise the following steps：
The raw material of the material containing Sr, the material containing Cd, the material containing Ge and simple substance S will be selected from according to mol ratio Sr:Cd:
Ge:S=1:1:1:4 ratio dispensing and after being well mixed, being heated to 750～850 DEG C carries out high temperature solid state reaction, obtains chemistry
Formula is SrCdGeS4Compound；Wherein, the material containing Sr is strontium simple substance or strontium sulfide, the material containing Cd be cadmium simple substance or
Cadmium sulfide, the material containing Ge is germanium simple substance or germanium disulfide.
Above-claimed cpd SrCdGeS4Preparation method in, the high temperature solid state reaction is comprised the concrete steps that：Match somebody with somebody described
Material is fitted in quartz ampoule, and to quartz ampoule 10 are evacuated to-3Pa simultaneously carries out fusing sealed knot, in being put into Muffle furnace, with 20～40 DEG C/h
Ramp to 750～850 DEG C, be incubated 96h, sample is taken out after cooling；Put again after the sample of taking-up is ground
10 are evacuated in quartz ampoule-3Pa simultaneously carries out fusing sealed knot, is put into afterwards in Muffle furnace and is warming up to 750～800 DEG C of sintering
48h；Sample is taken out after cooling, and grinding obtains powder SrCdGeS4Compound.
The SrCdGeS4Compound is successfully prepared by following chemical equations：
(1)SrS+CdS+GeS2=SrCdGeS4；
(2) SrS+Cd+Ge+3S=SrCdGeS4；
(3)SrS+Cd+GeS2+ S=SrCdGeS4；
(4) SrS+CdS+Ge+2S=SrCdGeS4；
(5) Sr+Cd+Ge+4S=SrCdGeS4；
(6) Sr+CdS+Ge+3S=SrCdGeS4。
Compound SrCdGeS4Infrared nonlinear optical crystal there is non-centrosymmetric structure, belong to rhombic system, space
Group is Ama2, and its cell parameter is：
α=β=γ=90 °, Z=4,
The invention provides compound SrCdGeS4Infrared nonlinear optical crystal two kinds of preparation methods：
The first：SrCdGeS is grown using horizontal gradient condensation method4Infrared nonlinear optical crystal, concretely comprise the following steps：
By powder SrCdGeS4Compound is enclosed in silica crucible, and is put in horizontal growth stove, the temperature of the horizontal growth stove
Gradient is 1～10 DEG C/cm, is heated to melting and keeps after 24～72h, with the movement of the speed of 5～10mm/ days thermal field make crystal by
Gradually grow, after crystal growth terminates, room temperature is down to the rate of temperature fall of 10～30 DEG C/h, obtain pale yellow transparent
SrCdGeS4Crystal.
Second：Using Bridgman-Stockbarge method for growing SrCdGeS4Infrared nonlinear optical crystal, concretely comprise the following steps：Will dress
There is powder SrCdGeS4The silica crucible of compound is put in crystal growing apparatus, is to slowly warm up to after powder is completely melt,
Silica crucible is vertically declined with the speed of 0.3～2.0mm/h, and during crucible declines SrCdGeS is carried out4Infrared non-linear
The growth of optical crystal, its growth cycle is 10～30d.
Above two method is adopted to obtain SrCdGeS of the size for Centimeter Level4Infrared nonlinear optical crystal；Use
The bigger crucible of size, while extending growth cycle, then can obtain corresponding large-size SrCdGeS4Infrared non-linear optics is brilliant
Body.
Prepare powder SrCdGeS that infrared nonlinear optical crystal is used4Compound is adopted and prepared with the following method：
By the material containing Sr, the material containing Cd, the material containing Ge and simple substance S according to mol ratio Sr:Cd:Ge:S=1:1:1:
4 ratio dispensing and after being well mixed, being heated to 750～850 DEG C carries out high temperature solid state reaction, obtains chemical formula for SrCdGeS4
Compound；Wherein, the material containing Sr is strontium simple substance or strontium sulfide, and the material containing Cd is cadmium simple substance or cadmium sulfide, containing Ge
Material be germanium simple substance or germanium disulfide.
The present invention still further provides compound SrCdGeS4Infrared nonlinear optical crystal purposes, should
SrCdGeS4Crystal can be used for preparing laser frequency device, and prepared laser frequency device is comprising sharp by least a branch of incidence
Light passes through at least one piece SrCdGeS4Device of at least a branch of frequency different from the radiant output of incident laser is produced after crystal.
Compared with prior art, the present invention at least has the advantages that：
The invention provides a kind of chemical formula is SrCdGeS4Novel infrared nonlinear optical crystal and preparation method thereof and
Purposes.In the SrCdGeS4The growing crystals of infrared nonlinear optical crystal are easily grown up and transparent without parcel, with growth speed
Degree is very fast, low cost, the advantages of be readily available large-size crystal；The SrCdGeS for being obtained4Infrared nonlinear optical crystal has
There are relatively wide infrared light transmission wave band, good mechanical property, easy to process and preservation.Infrared non-linear powder frequency doubling is tested
Show, in the case where fundamental frequency light is the irradiation of 2090nm laser, SrCdGeS4With strong nonlinear effect, in 41 μm～74 μm particle diameter models
Frequency-doubled signal intensity in enclosing is about with infrared classical materials A gGaS of particle diameter23 times of signal strength signal intensity.It is contemplated that, the present invention
The new infrared nonlinear optical crystal material SrCdGeS for being obtained4, there is potential application in infrared laser frequency transformation field
Value.
Description of the drawings
Fig. 1 is using SrCdGeS of the present invention4A kind of typical infrared non-linear light made by infrared nonlinear optical crystal
Learn the fundamental diagram of device；
Wherein 1 is infrared laser；2 laser beams that will be incided on crystal for representing 1 generation；3 is first piece of plated film
Mirror (mirror can pass through incident laser 2, be totally reflected crystal produce flashlight and ideler frequency light)；4 is after crystal
The SrCdGeS for meeting laser wavelength of incidence phase-matching condition after processing and processing4Crystal；5 is the mirror of second piece of plated film
(flashlight and ideler frequency light that the mirror can be produced partly through crystal, be totally reflected incident laser 2)；6 and 7 is the required of acquisition
The laser beam wanted.
Fig. 2 is SrCdGeS of the present invention4The structural representation of infrared nonlinear optical crystal.
Fig. 3 is SrCdGeS of the present invention4Experiment (Experimental) and (Simulated) powder x-ray diffraction being fitted
Collection of illustrative plates.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein is not used to only to explain the present invention
Limit the present invention.
Embodiment 1 prepares powder SrCdGeS4Compound
Using SrS+CdS+GeS2=SrCdGeS4Reaction equation prepares SrCdGeS with high-temperature solid phase reaction method4Compound；Institute
SrS is stated for 5.985 grams, the CdS is 7.224 grams, the GeS2For 6.837 grams；That is SrS:CdS:GeS2=0.05mol:
0.05mol:0.05mol。
Concrete operation step is to weigh reagent respectively by above-mentioned dosage in glove box, in placing them into mortar, mixing
And grind, in being then charged into the quartz ampoule of Φ 19mm × 25mm, it is evacuated to 10-3After Pa quartz ampoule fusing is sealed with oxyhydrogen flame
Dress, in being put into Muffle furnace, with the heating rate of 40 DEG C/h 800 DEG C is risen to, and is incubated 96h, sample is taken out after cooling and grinds mixed
It is even, then be placed in quartz ampoule and vacuumize encapsulation, 48h are sintered in 750 DEG C in Muffle furnace, sample shrinks blocking；It is drawn off, puts
To enter smash to pieces in mortar grinding and obtain powder SrCdGeS4Compound.
Embodiment 2 prepares powder SrCdGeS4Compound
Using SrS+Cd+Ge+3S=SrCdGeS4Reaction equation prepares SrCdGeS with high-temperature solid phase reaction method4Compound；Institute
SrS is stated for 5.985 grams, the Cd is 5.621 grams, the Ge is 3.631 grams, the S is 4.810 grams, i.e. SrS:Cd:Ge:S=
0.05mol:0.05mol:0.05mol:0.15mol；
Its concrete operation step is to weigh reagent respectively by above-mentioned dosage in glove box, be loaded into Φ 19mm ×
In the quartz ampoule of 25mm, 10 are evacuated to-3After Pa quartz ampoule fusing is encapsulated with flame, in being put into Muffle furnace, be slowly increased to 850
DEG C, its heating rate is 20 DEG C/h, is incubated 96h, is taken out after cooling, takes out sample and is ground, then is placed in quartz ampoule and takes out
Vacuum Package, 48h is sintered in Muffle furnace in 750 DEG C, and sample shrinks blocking；It is drawn off, is put into be smashed to pieces in mortar and grinds
To powder SrCdGeS4Compound.
Embodiment 3 prepares powder SrCdGeS4Compound
Using SrS+Cd+GeS2+ S=SrCdGeS4Reaction equation prepares SrCdGeS with high-temperature solid phase reaction method4Compound；Institute
SrS is stated for 5.985 grams, the Cd is 5.621 grams, the GeS2For 6.837 grams, the S is 1.603 grams, i.e. SrS:Cd:GeS2:
S=0.05mol:0.05mol:0.05mol:0.05mol；
Its concrete operation step is to weigh reagent respectively by above-mentioned dosage in glove box, be loaded into Φ 19mm ×
In the quartz ampoule of 25mm, 10 are evacuated to-3After Pa quartz ampoule fusing is encapsulated with flame, in being put into Muffle furnace, be slowly increased to 800
DEG C, its heating rate is 20 DEG C/h, is incubated 96h, is taken out after cooling, takes out sample and is ground, then is placed in quartz ampoule and takes out
Vacuum Package, 48h is sintered in Muffle furnace in 750 DEG C, and sample shrinks blocking；It is drawn off, is put into be smashed to pieces in mortar and grinds
To powder SrCdGeS4Compound.
Embodiment 4 prepares powder SrCdGeS4Compound
Using SrS+CdS+Ge+2S=SrCdGeS4Reaction equation prepares SrCdGeS with high-temperature solid phase reaction method4Compound；Institute
The SrS is 5.985 grams, and the CdS is 7.224 grams, and the Ge is 3.631 grams, and the S is 3.207 grams, i.e. SrS:CdS:
Ge:S=0.05mol:0.05mol:0.05mol:0.10mol；
Concrete operation step is to weigh reagent respectively by above-mentioned dosage in glove box, in placing them into mortar, mixing
And grind, in being then charged into the quartz ampoule of Φ 19mm × 25mm, it is evacuated to 10-3After Pa quartz ampoule fusing is sealed with oxyhydrogen flame
Dress, in being put into Muffle furnace, with the heating rate of 30 DEG C/h 800 DEG C is risen to, and is incubated 96h, sample is taken out after cooling and grinds mixed
It is even, then be placed in quartz ampoule and vacuumize encapsulation, 48h are sintered in 750 DEG C in Muffle furnace, sample shrinks blocking；It is drawn off, puts
To enter smash to pieces in mortar grinding and obtain powder SrCdGeS4Compound.
Embodiment 5 prepares powder SrCdGeS4Compound
Using Sr+Cd+Ge+4S=SrCdGeS4Reaction equation prepares SrCdGeS with high-temperature solid phase reaction method4Compound；It is described
Sr is 4.381 grams, and the Cd is 5.621 grams, and the Ge is 3.631 grams, and the S is 6.413 grams, i.e. Sr:Cd:Ge:S=
0.05mol:0.05mol:0.05mol:0.20mol；
Its concrete operation step is to weigh reagent respectively by above-mentioned dosage in glove box, be loaded into Φ 19mm ×
In the quartz ampoule of 25mm, 10 are evacuated to-3After Pa quartz ampoule fusing is encapsulated with flame, in being put into Muffle furnace, be slowly increased to 850
DEG C, its heating rate is 20 DEG C/h, constant temperature 96h, is taken out after cooling, takes out sample and is ground, then is placed in quartz ampoule and takes out
Vacuum Package, 48h is sintered in Muffle furnace in 800 DEG C, is drawn off, and is put in mortar and is ground prepared powder SrCdGeS4Change
Compound.
Embodiment 6 prepares powder SrCdGeS4Compound
Using Sr+CdS+Ge+3S=SrCdGeS4Reaction equation prepares SrCdGeS with high-temperature solid phase reaction method4Compound；Institute
Sr is stated for 4.381 grams, the CdS is 7.224 grams, the Ge is 3.631 grams, the S is 4.810 grams, i.e. Sr:CdS:Ge:S=
0.05mol:0.05mol:0.05mol:0.15mol；
Its concrete operation step is to weigh reagent respectively by above-mentioned dosage in glove box, be loaded into Φ 19mm ×
In the quartz ampoule of 25mm, 10 are evacuated to-3After Pa quartz ampoule fusing is encapsulated with flame, in being put into Muffle furnace, be slowly increased to 850
DEG C, its heating rate is 30 DEG C/h, constant temperature 96h, is taken out after cooling, takes out sample and is ground, then is placed in quartz ampoule and takes out
Vacuum Package, 48h is sintered in Muffle furnace in 750 DEG C, is drawn off, and is put in mortar and is ground prepared powder SrCdGeS4Change
Compound.
Embodiment 7 prepares SrCdGeS using horizontal gradient condensation method4Crystal
By the SrCdGeS obtained in embodiment 1 to 64Powder is fitted in the quartz ampoule of Φ 16mm × 20mm, is evacuated to 10-3After Pa, with (thermograde is 5～10 DEG C/cm) is placed in horizontal growth stove after oxyhydrogen flame encapsulation, being slowly increased to 1000 DEG C makes original
Expect to be completely melt and keep after 24～72h, with the speed movement thermal field of 5～10mm/ days (from crucible bottom to crucible top gradually
It is mobile) crystal growth is made, after crystal growth terminates, room temperature is cooled to 10～30 DEG C/h of rate of temperature fall, obtain faint yellow
Transparent SrCdGeS4Crystal.
Embodiment 8 prepares SrCdGeS using Bridgman-Stockbarger method4Crystal
By the SrCdGeS obtained in embodiment 1 to 64Powder is fitted in the silica crucible of Φ 16mm × 20mm, is evacuated to
10-3After Pa, with being placed in crystal growing apparatus after oxyhydrogen flame encapsulation, being slowly increased to 1000 DEG C is completely melt raw material and keeps 24
After～72h, silica crucible is vertically declined with the speed of 0.3～2.0mm/h, and during crucible declines SrCdGeS is carried out4It is infrared
Nonlinear optical crystal grows, and after crystal growth terminates, with the speed of 10～20 DEG C/h room temperature is cooled to, and obtains pale yellow transparent
SrCdGeS4Crystal.
Jing is tested, the SrCdGeS prepared by above-described embodiment 7～84Infrared nonlinear optical crystal has non-centrosymmetry
Structure, belongs to rhombic system, and space group is Ama2, and its cell parameter is： α=β=γ=90 °, Z=4,There is the crystal stronger powder frequency doubling to imitate
Should：In the case where fundamental frequency light is the irradiation of 2090nm laser, the frequency-doubled signal intensity in 41～74 μm of particle size ranges is about red with particle diameter
Outer classical materials A gGaS23 times of signal strength signal intensity.Fig. 2 is the SrCdGeS4The structural representation of infrared nonlinear optical crystal.
Fig. 3 is the SrCdGeS4Infrared nonlinear optical crystal is tested (Experimental) and is penetrated with (Simulated) powder X-ray of fitting
Ray diffraction diagram spectrum control.
Embodiment 9
By the SrCdGeS of the gained of embodiment 7 and 84Crystal be oriented, cut, polishing and plated film after, be placed on the institute of accompanying drawing 1
Showing device is numbered at 4 position, at room temperature, uses Nd:YAG laser makees light source, and incident wavelength is the infrared light of 1064nm,
Output wavelength is the frequency doubled light of 532nm.
Accompanying drawing 1 is using SrCdGeS of the present invention4A kind of typical infrared non-linear made by infrared nonlinear optical crystal
The fundamental diagram of optics, wherein 1 is infrared laser；2 laser beams that will be incided on crystal for representing 1 generation；3
It is the mirror (mirror can be totally reflected flashlight and ideler frequency light that crystal is produced through incident laser 2) of first piece of plated film；4
It is the SrCdGeS for meeting laser wavelength of incidence phase-matching condition after crystal post processing and optical manufacturing4Crystal；5 are
The mirror (flashlight and ideler frequency light that the mirror can be produced partly through crystal, be totally reflected incident laser 2) of second piece of plated film；
6 and 7 is the required laser beam for obtaining.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, however, it is to be understood that ability
Field technique personnel can be designed that a lot of other modification and embodiment, and these modifications and embodiment will fall public in the application
Within the spirit opened and spirit.
Claims (7)
1. a kind of compound, it is characterised in that its chemical formula is SrCdGeS4。
2. compound SrCdGeS4Preparation method, it is characterised in that it is comprised the following steps：
The raw material of the material containing Sr, the material containing Cd, the material containing Ge and simple substance S will be selected from according to elemental mole ratios Sr:Cd:
Ge:S=1:1:1:4 ratio dispensing and after being well mixed, being heated to 750～850 DEG C carries out high temperature solid state reaction, obtains chemistry
Formula is SrCdGeS4Compound；Wherein, the material containing Sr is strontium simple substance or strontium sulfide, the material containing Cd be cadmium simple substance or
Cadmium sulfide, the material containing Ge is germanium simple substance or germanium disulfide.
3. compound SrCdGeS according to claim 24Preparation method, it is characterised in that the high temperature solid state reaction
Comprise the concrete steps that：The dispensing is fitted in quartz ampoule, 10 are evacuated to quartz ampoule-3Pa simultaneously carries out fusing sealed knot, is put into horse
Not in stove, with the ramp of 20～40 DEG C/h to 750～850 DEG C, 96h is incubated, sample is taken out after cooling；The sample that will be taken out
Product are again placed in being evacuated to 10 in quartz ampoule after being ground-3Pa simultaneously carries out fusing sealed knot, is put into afterwards in Muffle furnace and heats up
To 750～800 DEG C of sintering 48h；Sample is taken out after cooling, and grinding obtains powder SrCdGeS4Compound.
4. compound SrCdGeS4Infrared nonlinear optical crystal, it is characterised in that the infrared nonlinear optical crystal belongs to orthogonal
Crystallographic system, space group is Ama2, and its cell parameter is： α=β=γ=90 °, Z=4,
5. compound SrCdGeS4Infrared nonlinear optical crystal preparation method, it is characterised in that using horizontal gradient condense
Method grows SrCdGeS4Infrared nonlinear optical crystal, concretely comprise the following steps：By powder as claimed in claim 3
SrCdGeS4Compound is enclosed in silica crucible, and is put in horizontal growth stove, and the thermograde of the horizontal growth stove is 1～
10 DEG C/cm, it is heated to melting and keeps after 24～72h, with the speed movement thermal field of 5～10mm/ days crystal is grown into, treats
After crystal growth terminates, room temperature is down to the rate of temperature fall of 10～30 DEG C/h, obtains the SrCdGeS of pale yellow transparent4Crystal.
6. compound SrCdGeS4Infrared nonlinear optical crystal preparation method, it is characterised in that using Bridgman-Stockbarger method give birth to
Long SrCdGeS4Infrared nonlinear optical crystal, concretely comprise the following steps：Will be equipped with powder as claimed in claim 3
SrCdGeS4The silica crucible of compound is put in crystal growing apparatus, is to slowly warm up to after powder is completely melt, silica crucible
Vertically declined with the speed of 0.3～2.0mm/h, during crucible declines SrCdGeS is carried out4Infrared nonlinear optical crystal
Growth, its growth cycle be 10～30d.
7. compound SrCdGeS4Infrared nonlinear optical crystal application, it is characterised in that it be used for prepare laser frequency converter
Part, prepared laser frequency device passes through at least one piece SrCdGeS comprising by least a branch of incident laser4Produce after crystal
At least a branch of frequency is different from the device of the radiant output of incident laser.
Priority Applications (1)
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| CN111118607A (en) * | 2020-01-08 | 2020-05-08 | 中国科学院上海硅酸盐研究所 | Hetero-anion nonlinear optical material and preparation method and application thereof |
| CN111118607B (en) * | 2020-01-08 | 2021-07-13 | 中国科学院上海硅酸盐研究所 | Hetero-anion nonlinear optical material and preparation method and application thereof |
| CN112080802A (en) * | 2020-08-11 | 2020-12-15 | 三明学院 | Infrared nonlinear optical crystal with high laser damage threshold value, preparation and application |
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