CN1951820A - Non-center-symmetrical structure rare earth sulfide - Google Patents
Non-center-symmetrical structure rare earth sulfide Download PDFInfo
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- CN1951820A CN1951820A CN 200510118211 CN200510118211A CN1951820A CN 1951820 A CN1951820 A CN 1951820A CN 200510118211 CN200510118211 CN 200510118211 CN 200510118211 A CN200510118211 A CN 200510118211A CN 1951820 A CN1951820 A CN 1951820A
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Abstract
The invention discloses a non-center asymmetrical rare-earth sulfide synthesizing method, crystal growth and application, which contains La6Ag2Sn2S7, a6Ge2x+2S14, La6Sn2x+2S14 (x=1/4-1/2). The sulfide can be applied to prepare infrared non-linear optical element, which is synthesized by alkaline metal halide flux technique.
Description
Technical field
The present invention relates to La
6Ag
2Sn
2S
7, La
6Ge
2x+2S
14, La
6Sn
2x+2S
14(x=1/4-1/2) synthetic, the crystal growth of compound and application
Background technology
The infrared non-linear optical material can be used for making frequency doubling device, and the broadband is adjustable infrared parametric oscillator carries out the range finding of mixing and optical parametric oscillation and infrared remote, has been widely used at aspects such as laser communications and military technique and infrared telemetrys.In recent years, along with CO
2Technology rapid development such as lidar detection, infrared telemetry, laser communications, infrared navigation, more and more urgent to the requirement of high quality, high-performance infrared non-linear optical material.
Chalcogen compound makes them become the elite clone of long wave transmission in the characteristic absorbance of low-frequency range.Chalcogenide materials has and extends to far optical clear characteristic.Many useful sulfide materials have from the transmission window of 0.5 to 14um scope.The chalcogen compound of no core structure can be used as the second-order non-linear optical materials that uses at region of ultra-red, and is especially interesting.Had been found that many chalcogen compounds of taking the non-centrosymmetry spacer at present, the sulfide material of some nonlinear optical properties, for example, AgGaS
2, LiInS
2, LiGaQ
2(Q=S, Se Te) are familiar with by people.
The desirable properties of nonlinear optical material comprises big non-linear susceptibility, transparent, the high light injury threshold of (using ω and 2 ω for frequency multiplication) in the work area, machinery, chemistry, thermostability and be easy to mix and processing.And rare earth chalcogen compound has excellent thermostability, intensity and infrared transmission characteristic, and therefore non-centrosymmetrical rare earth chalcogen compound may become the second order infrared non-linear optical material of the new excellent performance of a class.
R
6B
2C
2Q
14(Q=S is that a space-like group is P6 Se)
3Rare earth chalcogen compound, R is a rare earth element, B is generally the hexa-coordinate metallic element, C is the four-coordination element.This compounds is synthesized by people such as Guittard at first.In many cases, the general molecular formula of this class is R
6B
2C
2Q
14Compound because positively charged ion, anionic charge equilibrated need, exist the room.Defective compound known today has following composition R
6(B
n 2-n) C
2Q
14, is the room, n=1/2,2/3,1 and 4/3.
Summary of the invention:
We select rare-earth elements La, and four-coordination element Ge or Sn prepare precursor and synthetic and 3 the new sulfide La that grown by alkali metal halide fusing assistant technology by high temperature solid state reaction
6Ag
2Sn
2S
14, La
6Ge
2x+2S
14, La
6Sn
2x+2S
14(x=x=1/4-1/2) crystal.La
6Ge
2x+2S
14, La
6Sn
2x+2S
14(x=1/4-1/2) be the defective compound, in their crystalline structure, the position of C is occupied by Ge (IV) or Sn (IV), and the position of B can be occupied by Ge (II), Ge (IV) or Sn (II), Sn (IV), and their molecular formula can be written as La
6Ge
2xGe
2S
14, La
6Sn
2xSn
2S
14(x=1/4-1/2).
La
6Ag
2Sn
2S
7: spacer is P6
3(No.163), cell parameter is a=b=10.378 (2) , c=5.990 (1) , Z=1, unit-cell volume V=558.7 (2)
3
La
6Ge
2x+2S
14(x=1/4-1/2): spacer is P6
3(No.163), cell parameter is a=b=10.297 (2) , c=5.812 (1) , Z=2, unit-cell volume V=533.7 (2)
3
La
6Sn
2x+2S
14(x=1/4-1/2): spacer is P6
3(No.163), cell parameter is a=b=10.277 (2) , c=6.003 (1) , Z=2, unit-cell volume V=549.1 (2)
3
Sulfide La provided by the invention
6Ag
2Sn
2S
14, La
6Ge
2x+2S
14, La
6Sn
2x+2S
14(x=1/4-1/2) crystal prepares precursor by high temperature solid state reaction and is that fusing assistant carries out crystal growth with the alkali metal halide.The optional KBr of fusing assistant, NaBr, KCl, NaCl.
In the high temperature solid state reaction process, raw material is warming up to 900-1200 ℃, after constant temperature, mixture fully react, is cooled to room temperature naturally.With the alkali metal halide is fusing assistant, utilizes the aforementioned precursor for preparing to carry out crystal growth, is warming up to more than the fusing assistant fusing point, behind the long-time constant temperature, and cooling naturally.
Non-centrosymmetrical rare earth chalcogen compound may become the second order infrared non-linear optical material of the new excellent performance of a class.The sulfide La of the present invention's preparation
6Ag
2Sn
2S
14, La
6Ge
2x+2S
14, La
6Sn
2x+2S
14(x=1/4-1/2) crystal can be used for making infrared non-linear optics element.
Embodiment
1.La
6Ag
2Sn
2S
14
Under the high pure nitrogen atmosphere protection, press La
2S
3: Ag
2S: SnS
2=3: 1: 2 mol ratio takes by weighing 0.13584g (mmol) La
2S
3, 0.03g (mmol) Ag
2S, 0.4422g (mmol) SnS
2, compressing tablet after grinding, mixing in the silica tube of the end of packing into sealing, seals with oxyhydrogen flame under dynamic vacuum subsequently.This reaction tubes is placed in the high temperature reaction stove, and be warming up to 750 ℃ with the speed of 20 ℃/hr, constant temperature was warming up to 1000 ℃ with identical speed after 24 hours, and constant temperature 240 hours is to allow mixture fully react.Turn off power supply, be cooled to room temperature naturally.Take out reaction tubes, take out reaction tubes, after opening reaction mixture is ground with 0.80g KBr, mix, then this precursor/fusing assistant mixture is resealed in the silica tube that vacuumizes.This reaction tubes is placed in the high temperature reaction stove, and be warming up to 850 ℃ with the speed of 15 ℃/hr, constant temperature is after 15 days, is cooled to 650 ℃ with the speed of 1.5 ℃/hr, turns off power supply, is cooled to room temperature naturally.Take out reaction tubes, after opening reaction mixture is soaked in distilled water, filter, hand goes out red granular crystal.Analyze through the X ray single crystal diffraction, determine that red granular crystal is La
6Ag
2Sn
2S
14EDX analysis revealed crystal only contains La, Ag, Sn, S, does not detect K, Br.
2.La
6Ge
2x+2S
14(x＝1/4-1/2)
Under the high pure nitrogen atmosphere protection, press La
2S
3: Al: Ge: S=1: 2: 2: 7 mol ratio takes by weighing 0.1039g (0.278mmol) La
2S
3, 0.15g (0.556mmol) Al, 0.4037g (0.556mmol) Ge, 0.0624g (1.946mmol) S, compressing tablet after grinding, mixing in the plating carbon silica tube of the end of packing into sealing, and adds a spot of iodine, seals with oxyhydrogen flame under dynamic vacuum subsequently.This reaction tubes is placed in the high temperature reaction stove, and be warming up to 700 ℃ with the speed of 18 ℃/hr, constant temperature was warming up to 1000 ℃ with identical speed after 24 hours, and constant temperature 10 days is cooled to 640 ℃ with the speed of 2 ℃/hr, turns off power supply, is cooled to room temperature naturally.Take out reaction tubes, after opening reaction mixture is ground with 0.80g NaBr, mix, then this precursor/fusing assistant mixture is resealed in the silica tube that vacuumizes.This reaction tubes is placed in the high temperature reaction stove, and be warming up to 850 ℃ with the speed of 15 ℃/hr, constant temperature is after 10 days, is cooled to 700 ℃ with the speed of 1.5 ℃/hr, turns off power supply, is cooled to room temperature naturally.Take out reaction tubes, after opening reaction mixture is soaked in distilled water, filter, hand goes out the granular crystal of garnet.Analyze through the X ray single crystal diffraction, determine the granular La of being of garnet
6Ge
2x+2S
14(x=1/4-1/2).EDX analysis revealed crystal only contains La, Ge, S, does not detect other elements such as Na, Al, Br, I.
3.La
6Sn
2xSn
2S
14(x＝1/4-1/2)
Under the high pure nitrogen atmosphere protection, press La
2S
3: Na
2S: SnS
2=3: 1: 2 mol ratio takes by weighing 0.2874g (0.768mmol) La
2S
3, 0.02g (0.256mmol) Na
2S, 0.0936g (0.512mmol) SnS
2, compressing tablet after grinding, mixing in the plating carbon silica tube of the end of packing into sealing, seals with oxyhydrogen flame under dynamic vacuum subsequently.This reaction tubes is placed in the high temperature reaction stove, and be warming up to 750 ℃ with the speed of 5 ℃/hr, constant temperature is after 80 hours, is warming up to 1000 ℃ with the speed of 10 ℃/hr, and constant temperature 6 days is cooled to 380 ℃ with the speed of 2.87 ℃/hr, turns off power supply, is cooled to room temperature naturally.Take out reaction tubes, after opening reaction mixture is ground with 0.80g NaBr, mix, then this precursor/fusing assistant mixture is resealed in the silica tube that vacuumizes.This reaction tubes is placed in the high temperature reaction stove, and be warming up to 830 ℃ with the speed of 12.4 ℃/hr, constant temperature is after 8 days, is cooled to 700 ℃ with the speed of 2 ℃/hr, turns off power supply, is cooled to room temperature naturally.Take out reaction tubes, after opening reaction mixture is soaked in distilled water, filter, hand goes out reddish brown granular crystal.Analyze through the X ray single crystal diffraction, determine that black granular crystal is La
6Sn
2xSn
2S
14(x=1/4-1/2).EDX analysis revealed crystal only contains La, Sn, S, does not detect Na, Br.
Claims (5)
1. non-centrosymmetry structure rare-earth sulfide is characterized in that: this sulfide chemical formula is La
6Ag
2Sn
2S
7, spacer is P6
3(No.163), cell parameter is a=b=10.378 (2) , c=5.990 (1) , Z=1, unit-cell volume V=558.7 (2)
3
2. non-centrosymmetry structure rare-earth sulfide is characterized in that: this sulfide chemical formula is La
6Ge
2x+2S
14(x=1/4-1/2), spacer is P6
3(No.163), cell parameter is a=b=10.297 (2) , c=5.812 (1) , Z=2, unit-cell volume V=533.7 (2)
3
3. non-centrosymmetry structure rare-earth sulfide is characterized in that: this sulfide chemical formula is La
6Sn
2x+2S
14(x=1/4-1/2), spacer is P6
3(No.163), cell parameter is a=b=10.277 (2) , c=6.003 (1) , Z=2, unit-cell volume V=549.1 (2)
3
4. claim 1 or 2 or 3 sulfide crystalline preparation method is characterized in that: prepare precursor and be that fusing assistant carries out crystal growth with the alkali metal halide by high temperature solid state reaction.
5. 1 of a claim 1 or 2 or 3 sulfide crystalline purposes, it is characterized in that: this crystal is used to make infrared non-linear optics element.
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|---|---|---|---|
| CN 200510118211 CN1951820A (en) | 2005-10-20 | 2005-10-20 | Non-center-symmetrical structure rare earth sulfide |
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|---|---|---|---|
| CN 200510118211 CN1951820A (en) | 2005-10-20 | 2005-10-20 | Non-center-symmetrical structure rare earth sulfide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676032B (en) * | 2008-09-16 | 2013-02-06 | 中国科学院福建物质结构研究所 | Ge-Sb micropore sulfide with ion exchange performance, preparation method and usage thereof |
| CN103103612A (en) * | 2011-11-09 | 2013-05-15 | 中国科学院福建物质结构研究所 | Non-centrosymmetric rare-earth sulfide containing Mg |
| CN106757303A (en) * | 2012-06-11 | 2017-05-31 | 中国科学院福建物质结构研究所 | Monoclinic phase Ga2S3The preparation method of crystal and its application optically |
| CN109778317A (en) * | 2019-01-24 | 2019-05-21 | 中国科学院福建物质结构研究所 | A kind of crystalline material and the preparation method and application thereof of the non-heart sulfide of quaternary |
-
2005
- 2005-10-20 CN CN 200510118211 patent/CN1951820A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676032B (en) * | 2008-09-16 | 2013-02-06 | 中国科学院福建物质结构研究所 | Ge-Sb micropore sulfide with ion exchange performance, preparation method and usage thereof |
| CN103103612A (en) * | 2011-11-09 | 2013-05-15 | 中国科学院福建物质结构研究所 | Non-centrosymmetric rare-earth sulfide containing Mg |
| CN103103612B (en) * | 2011-11-09 | 2016-08-03 | 中国科学院福建物质结构研究所 | Containing Mg non-center-symmetrical structure rare earth sulfide |
| CN106757303A (en) * | 2012-06-11 | 2017-05-31 | 中国科学院福建物质结构研究所 | Monoclinic phase Ga2S3The preparation method of crystal and its application optically |
| CN109778317A (en) * | 2019-01-24 | 2019-05-21 | 中国科学院福建物质结构研究所 | A kind of crystalline material and the preparation method and application thereof of the non-heart sulfide of quaternary |
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Application publication date: 20070425 |