CN106835283B - Sulphur antimony sodium barium optical crystal and preparation method and purposes - Google Patents
Sulphur antimony sodium barium optical crystal and preparation method and purposes Download PDFInfo
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- CN106835283B CN106835283B CN201510882747.9A CN201510882747A CN106835283B CN 106835283 B CN106835283 B CN 106835283B CN 201510882747 A CN201510882747 A CN 201510882747A CN 106835283 B CN106835283 B CN 106835283B
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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
- 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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- 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
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Abstract
The present invention relates to a kind of sulphur antimony sodium barium optical crystal and preparation method and purposes, which is BaNaSbS3, molecular weight 378.26 belongs to monoclinic system, and space group P21/C, cell parameter is a=6.0668(16), b=14.232 (4), c=7.778 (2), V=646.9 (3)3, Z=4.It is made of high temperature solid-state method, the sulphur antimony sodium crystal of barium that the method obtains through the invention, the crystal is stable in the air, it is not easy to deliquesce, it is not soluble in water, there is good transmission in mid and far infrared wave band 3-20 μ m, it can be used as optical lens, have potential application in optics and communication field.
Description
Technical field
It is BaNaSbS the present invention relates to chemical formula3Sulfide sulfur antimony sodium barium optical crystal, crystal preparation method and use
On the way.
Background technique
New infrared optical material is explored always to be the hot spot of research.Since mid and far infrared coherent source is in infrared doctor
The civil field such as treatment, infrared detection, infrared spectrum analysis is applied, at the same laser orientation infrared counteraction, laser guidance, swash
The military fields such as optical communication, infrared remote sensing also have important application.The optical material haveing excellent performance in order to obtain needs to continue
It is explored.The selection of the following infrared optical material mainly considers both sides performance.(1) there is high laser damage threshold；
(2) there is high transmitance in mid and far infrared wavelength band.And alkaline-earth metal and metal sulfide have above-mentioned two respectively
The excellent performance of kind.On this basis, people have explored some compounds, such as BaSb2S4/Se4、Ba8Sb6S17、
Ba4Sb4Se11、Na2Ba3Sb4Deng although these compounds have relatively good structure, especially Na2Ba3Sb4It is in β-Ba5Sb4Change
It closes due to the distortion of cation in object structure, replacement generates new compound, has potential application in terms of diamagnetism, but red
The material needs of outer optical field continue to explore, and alkali metal is incorporated herein, and so that its structure is generated distortion, and widen band gap,
Thus alkaline earth sulfide becomes more promising infrared optical material.
In Development of Novel crystal for infrared use, people still select transparency range wide, the big alkaline earth of laser damage threshold
Metal sulfide crystal, and in order to further widen transparency range, increase laser damage threshold, cation is usually used not to be had
There is the alkali or alkaline earth metal of d-d electron transition.
Summary of the invention
The object of the present invention is to provide a kind of sulphur antimony sodium crystal of barium for mid and far infrared wave section, chemical formula is
BaNaSbS3, it is wide (3-20 μm) through range, and mid and far infrared wave band can be used for.
Another object of the present invention is to provide the preparation methods of sulphur antimony sodium crystal of barium.
A further object of the present invention is to provide the purposes of the sulphur antimony sodium crystal of barium.
A kind of sulphur antimony sodium barium optical crystal of the present invention, the chemical formula of the crystal are BaNaSbS3, molecular weight
378.26, belong to monoclinic system, space group P21/ C, cell parameter are
The preparation method of the sulphur antimony sodium barium optical crystal, is synthesized, concrete operations are pressed using high temperature solid phase synthesis
Column step carries out:
A, one-step synthesis is selected: by Ba, Na, Sb or Sb2S3, S metal simple-substance as raw material, Ba:Na:Sb in molar ratio:
S=1:1:0.5-1:1.5-3 weighs mixing, and mixture is put into graphite crucible；
Or select step synthesis synthesis: Ba:S=1:1 being weighed mix in molar ratio, mixture is put into graphite crucible
In, intermediate product BaS is synthesized, using obtained BaS intermediate product as raw material, BaS:Na:Sb or Sb in molar ratio2S3: S=1:
1:0.5-1:0.5-2 weighs mixing, and mixture is put into graphite crucible；
B, graphite crucible is put into silica quartz pipe, blowtorch and vacuum molecule pump assembly is selected to carry out tube sealing operation,
Blowtorch is provided combustion-supporting using oxygen and methane gas, in vacuum degree is 10 by silica quartz pipe-2-10-4Pa operating environment condition
Lower carry out tube sealing；
C, the silica quartz pipe sealed is placed on sintering inside Muffle furnace, heating temperature is to 450-800 DEG C, constant temperature
40-65 hours, room temperature is then dropped to, silica quartz pipe is taken out from burner hearth, separates crystal from graphite crucible
Obtain sulphur antimony sodium barium optical crystal.
Purposes of the sulphur antimony sodium barium optical crystal in preparation Infrared Therapy, infrared detection, infrared spectrum analysis.
Use in laser orientation infrared counteraction, laser guidance, laser communications or infrared remote sensing involved in the infrared detection
On the way.
A kind of sulphur antimony sodium barium optical crystal of the present invention and preparation method and purposes, wherein the crystal-chemical formula be
BaNaSbS3, molecular weight 378.26 belongs to monoclinic system, space group P21/C, and cell parameter is Z=4.
The sulphur antimony sodium crystal of barium, is 3-20 μm through range；It is stable in the air, it is not easy to deliquesce, it is not soluble in water.
Metal simple-substance Ba, Na, Sb, S or Sb in the sulphur antimony sodium barium optical crystal2S3It is described for purity 99.9%
S purity is 99.9%.
Advantages of the present invention is as follows: the transmission range of sulphur antimony sodium crystal of barium of the present invention is wide, and remote red in can be used for
Outer wave section (3-20 μm)oIt is stable in the air, it does not deliquesce, it is not soluble in water.There is potential application in optics and communication field.
Detailed description of the invention
Fig. 1 is BaNaSbS of the present invention3Sulphur antimony sodium barium X-ray diffraction figure；
Fig. 2 is BaNaSbS of the present invention3Sulphur antimony sodium crystal of barium structure chart；
Fig. 3 is BaNaSbS of the present invention3Crystal can be used in the working principle diagram of optical lens, wherein 1 is laser, 2 are
Focusing system, 3 be BaNaSbS3Crystal, 4 be grating prism, and 5 be filter plate.
Specific embodiment
Embodiment 1
By chemical equation: Ba+Na+Sb+3S → BaNaSbS3Crystal is prepared, raw materials used (analysis is pure):
A, it selects one-step synthesis: in molar ratio claiming Ba 0.137g, Na 0.023g, Sb 0.112g and S 0.096g
Amount mixing, then mixture is put into graphite crucible；
B, step a graphite crucible is put into silica quartz pipe, blowtorch and vacuum molecule pump assembly is selected to carry out tube sealing
Operation, blowtorch are provided combustion-supporting using oxygen and methane gas, in vacuum degree are 10 by silica quartz pipe-2-10-4Pa operates ring
Tube sealing is carried out under the conditions of border；
C, the silica quartz pipe that step b is sealed is placed on sintering inside Muffle furnace, heating temperature is to 450 DEG C, constant temperature
40 hours, room temperature is then dropped to, silica quartz pipe is taken out from burner hearth, crystal is separated from graphite crucible, can be obtained
To sulphur antimony sodium barium BaNaSbS3Optical crystal.
Embodiment 2
By chemical equation: Ba+Na+1/2Sb2S3+3/2S→BaNaSbS3Crystal is prepared, raw materials used (analysis is pure):
A, one-step synthesis is selected: in molar ratio by Ba 0.137g, Na 0.023g, Sb2S30.160g and S 0.048g
Mixing is weighed, mixture is put into graphite crucible；
B, graphite crucible is put into silica quartz pipe, blowtorch and vacuum molecule pump assembly is selected to carry out tube sealing operation,
Blowtorch is provided combustion-supporting using oxygen and methane gas, in vacuum degree is 10 by silica quartz pipe-2-10-4Pa operating environment condition
Lower carry out tube sealing；
C, the silica quartz pipe sealed is placed on sintering inside Muffle furnace, for heating temperature to 500 DEG C, constant temperature 50 is small
When, room temperature is then dropped to, silica quartz pipe is taken out from burner hearth, crystal is separated from graphite crucible, sulphur can be obtained
Antimony sodium barium BaNaSbS3Optical crystal.
Embodiment 3
Step 1: chemical equation: Ba+S → BaS, step 2: chemical equation: BaS+Na+Sb+2S → BaNaSbS3
Crystal is prepared, raw materials used (analysis is pure):
A, it selects step synthesis synthesis: Ba 0.137g, S 0.032g being weighed mix in molar ratio, mixture is put
Enter in graphite crucible, synthesize intermediate product BaS, using obtained BaS intermediate product as raw material, in molar ratio BaS 0.169g,
Na 0.023g, Sb 0.112g and S 0.064g weigh mixing, and mixture is put into graphite crucible；
B, graphite crucible is put into silica quartz pipe, blowtorch and vacuum molecule pump assembly is selected to carry out tube sealing operation,
Blowtorch is provided combustion-supporting using oxygen and methane gas, in vacuum degree is 10 by silica quartz pipe-2-10-4Pa operating environment condition
Lower carry out tube sealing；
C, the silica quartz pipe sealed is placed on sintering inside Muffle furnace, for heating temperature to 700 DEG C, constant temperature 60 is small
When, room temperature is then dropped to, silica quartz pipe is taken out from burner hearth, crystal is separated from graphite crucible, sulphur can be obtained
Antimony sodium barium BaNaSbS3Optical crystal.
Embodiment 4
Step 1: chemical equation: Ba+S → BaS, step 2: chemical equation: BaS+Na+1/2Sb2S3+1/2S→
BaNaSbS3Crystal is prepared, raw materials used (analysis is pure):
A, it selects step synthesis synthesis: Ba 0.137g, S 0.032g being weighed mix in molar ratio, mixture is put
Enter in graphite crucible, synthesize intermediate product BaS, using obtained BaS intermediate product as raw material, in molar ratio BaS 0.169g,
Na 0.023g、Sb2S30.160g and S 0.016g weighs mixing, and mixture is put into graphite crucible；
B, graphite crucible is put into silica quartz pipe, blowtorch and vacuum molecule pump assembly is selected to carry out tube sealing operation,
Blowtorch is provided combustion-supporting using oxygen and methane gas, in vacuum degree is 10 by silica quartz pipe-2-10-4Pa operating environment condition
Lower carry out tube sealing；
C, the silica quartz pipe sealed is placed on sintering inside Muffle furnace, for heating temperature to 800 DEG C, constant temperature 65 is small
When, room temperature is then dropped to, silica quartz pipe is taken out from burner hearth, crystal is separated from graphite crucible, sulphur can be obtained
Antimony sodium barium BaNaSbS3Optical crystal.
Embodiment 5
By arbitrary BaNaSbS obtained by embodiment 1-43Crystal is placed on 3 position as shown in attached drawing 3, in room temperature
Under, with Q Nd:YAG laser light source is adjusted, incident wavelength 1064nm, issuing wavelength by tune Q Nd:YAG laser 1 is
The infrared beam of 1064nm is incident on BaNaSbS after line focus system 23Monocrystalline 3, after grating prism 4 and filter plate 5, output
Laser with high transmitance shows that the crystal has high transmitance at 3-20 μm, can be used as optical lens.
Claims (4)
1. a kind of sulphur antimony sodium barium optical crystal, it is characterised in that the chemical formula of the crystal is BaNaSbS3, molecular weight 378.26, category
In monoclinic system, space group P21/ C, cell parameter are a=6.0668(16), b=14.232 (4), c=7.778
(2), V=646.9 (3)3。
2. the preparation method of sulphur antimony sodium barium optical crystal according to claim 1, it is characterised in that closed using high temperature solid-state
It is synthesized at method, concrete operations follow these steps to carry out:
A, one-step synthesis is selected: by Ba, Na, Sb or Sb2S3, S metal simple-substance as raw material, Ba:Na:Sb:S=1 in molar ratio:
1:0.5-1:1.5-3 weighs mixing, and mixture is put into graphite crucible；
Or select step synthesis synthesis: Ba:S=1:1 being weighed mix in molar ratio, mixture is put into graphite crucible, closes
At intermediate product BaS, using obtained BaS intermediate product as raw material, BaS:Na:Sb or Sb in molar ratio2S3:S=1:1: 0.5-
1:0.5-2 weighs mixing, and mixture is put into graphite crucible；
B, graphite crucible is put into silica quartz pipe, blowtorch and vacuum molecule pump assembly is selected to carry out tube sealing operation, blowtorch
It is provided using oxygen and methane gas combustion-supporting, in vacuum degree is 10 by silica quartz pipe-2-10-4Under the conditions of Pa operating environment into
Row tube sealing；
C, the silica quartz pipe sealed is placed on sintering inside Muffle furnace, heating temperature is to 450-800 DEG C, constant temperature 40-65
Hour, room temperature is then dropped to, silica quartz pipe is taken out from burner hearth, crystal is separated from graphite crucible, can be obtained
Sulphur antimony sodium barium optical crystal.
3. purposes of the sulphur antimony sodium barium optical crystal according to claim 1 in infrared detection, infrared spectrum analysis.
4. purposes according to claim 3, it is characterised in that laser orientation infrared counteraction involved in the infrared detection swashs
Purposes in light guide, laser communications or infrared remote sensing.
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| CN111285398A (en) * | 2020-03-26 | 2020-06-16 | 中国科学院新疆理化技术研究所 | Antimony strontium lithium sulfide infrared double refraction crystal and its preparation method and use |
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| CN102644117A (en) * | 2012-04-27 | 2012-08-22 | 中国科学院福建物质结构研究所 | Selenium indium bismuth barium single crystal, preparation and application thereof |
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2015
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Patent Citations (10)
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|---|---|---|---|---|
| EP0398503A2 (en) * | 1989-04-19 | 1990-11-22 | Her Majesty The Queen In Right Of New Zealand | Rare-earth barium copper oxide superconducting materials |
| JP2000199882A (en) * | 1998-12-29 | 2000-07-18 | Tokin Corp | Low-loss magneto-optical element and its production |
| JP2001233699A (en) * | 2000-02-25 | 2001-08-28 | Sumitomo Electric Ind Ltd | Method for thermally treating group ii to vi compound semiconductor crystal substrate and the substrate |
| US6514336B1 (en) * | 2000-10-12 | 2003-02-04 | Utar Scientific, Inc. | Method of growing piezoelectric lanthanide gallium crystals |
| CN1846291A (en) * | 2003-08-02 | 2006-10-11 | 磷光体技术公司 | Light emitting devices having sulfoselenide fluorescent phosphors |
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