CN102515530A - Mid-infrared luminescent chalcohalide glass and preparation technology thereof - Google Patents
Mid-infrared luminescent chalcohalide glass and preparation technology thereof Download PDFInfo
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- CN102515530A CN102515530A CN2011104009336A CN201110400933A CN102515530A CN 102515530 A CN102515530 A CN 102515530A CN 2011104009336 A CN2011104009336 A CN 2011104009336A CN 201110400933 A CN201110400933 A CN 201110400933A CN 102515530 A CN102515530 A CN 102515530A
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Abstract
The invention discloses a 2.7 mu m mid-infrared luminescent chalcohalide glass and a preparation technology thereof. The glass is prepared by using a melt quenching method and comprises the following components expressed in mole percent: 50 to 70 mol% of GeS2, 15 to 35 mol% of Ga2S3, 5 to 15 mol% of CsCl, 0.1 to 0.5 mol% of Er2S3 and 0 to 0.15 mol% of Nd2S3 (wherein the total content of all the components is 100 mol%). Since the mid-infrared luminescent chalcohalide glass has extraordinary infrared transmittance and good thermal and mechanical performances, the mid-infrared luminescent chalcohalide glass is expected to be applied in fabrication of 2.7 mu m mid-infrared lasers.
Description
Technical field
The present invention relates to the optical material field, relate in particular to infraluminescence sulfur-halogen glass and technology of preparing thereof in a kind of 2.7 microns.
Technical background
Er
3+:
4I
11/2→
4I
13/2The maximum absorption band position consistency of middle infraluminescence wave band and water molecules is a most important wave band in the laser medicine, in nearly many decades, is getting more and more people's extensive concerning always.In the tissue of biological cells, the content of moisture accounts for 70% at least, and no matter laser is to make the tissue element fracture through Photochemical effects to the effect of human body, still makes tissue vaporization's incising cell through heat effect, all requires histocyte can fully absorb laser energy.Commercial YAG:Er
3+Laser apparatus has been widely used in fields such as dental operation, oral surgery, laser beautifying.The research proof, the mid-infrared laser of this wave band is shallow to the histocyte penetration depth, and is little to the thermal damage and the physical abuse of human body.In order to obtain stronger Er
3+:
4I
11/2→
4I
13/2Laser emission, generally need satisfy following condition: have suitable phonon energy body material, have the sensitized ions of big absorption cross and Er
3+:
4I
13/2Energy level can effectively move back population to realize population inversion.
At present, people have studied Er in different body materials
3+:
4I
11/2→
4I
13/2Middle infraluminescence.For example, in calcium aluminate glass and fluoride glass, realized Yb respectively
3+Sensitization enhanced Er
3+Middle infraluminescence; In tellurate glass, realized Nd
3+Sensitization enhanced Er
3+Middle infraluminescence.It should be noted that these glass basiss with high phonon energy will make Er
3+:
4I
11/2Energy level moves back population through the mode of radiationless relaxation, thereby reduces wherein infraluminescence efficient greatly.The chalcogenide glass of gallium base has very low phonon energy (250cm
-1-400cm
-1), the good middle-infrared band transparency and higher rare earth ion solid solubility, thereby be to realize Er
3+The desirable body material of middle infraluminescence.When haloid element is introduced in the glass ingredient, it will get into the glass network structure, and the local coordination environment that makes rare earth ion is from [GaS
4] tetrahedron is to [GaS
3/2X]
-(I) tetrahedron changes for X=Cl, Br.Because [GaS
3/2X]
-Group has lower phonon energy, and the middle infraluminescence efficient of rare earth ion is expected to obtain to promote significantly.The present invention adopts the melt supercooled legal system to be equipped with Nd
3+/ Er
3+The Ga that mixes altogether
2S
3-GeS
2The transparent sulfur-halogen glass of-CsCl.In this material, Nd
3+Ion can pass through Nd effectively
3+:
4F
3/2Energy level is to Er
3+:
4I
11/2Energy level transmits energy, thereby promotes Er
3+:
4I
11/2→
4I
13/2Middle infraluminescence.
Summary of the invention
The present invention proposes infraluminescence sulfur-halogen glass and technology of preparing thereof in a kind of 2.7 microns, and purpose is to prepare the glass composition containing sulfure halide material that has good mechanical, calorifics and optical property, has the important application prospect in the laser medicine field.
Sulfur-halogen glass component of the present invention and molar content are following:
GeS
2: 50-70mol%; Ga
2S
3: 15-35mol%; CsCl:5-15mol%; Er
2S
3: 0.1-0.5mol%; Nd
2S
3: 0-0.15mol% (above-mentioned each component concentration sum is 100mol%).
Technical scheme of the present invention is following:
Highly purified germanium powder (5N), gallium piece (5N), sulphur powder (5N), cesium chloride (4N), sulfuration erbium (4N) and ncodymium sulfide raw materials such as (4N) are carried out accurate weighing according to certain set of dispense than in glove box, then be transferred in the end quartz ampoule that sealing by fusing is good, 10
-2Carry out tube sealing with oxyhydrogen flame under the vacuum condition of Pa; Subsequently, place tubular type to wave stove the quartz ampoule that sample is housed, be incubated 12～24h down at 900 ℃～1100 ℃, and follow and wave, even to guarantee the reactant thorough mixing; The quartz ampoule that through water-cooled fusing sample is housed at last obtains sulfur-halogen glass, and will prepared sulfur-halogen glass places 280 ℃ (under second-order transition temperatures 100 ℃) to anneal with the elimination internal stress.
Sulfur-halogen glass preparation technology of the present invention is simple, with low cost, is expected to be applied to 2.7 microns middle infrared lasers.
Description of drawings
Fig. 1 is the X-ray diffractogram of sulfur-halogen glass sample in the instance 1;
Fig. 2 is the absorption spectrum of sulfur-halogen glass sample in the instance 1;
Fig. 3 is the middle infra-red emission of sulfur-halogen glass sample under 808 excited in the instance 1.
Embodiment
Instance 1: with Ge (99.999%), Ga (99.99%), S (99.999%), CsCl (99.9%), Nd
2S
3(99.9%) and Er
2S
3(99.9%) high pure raw material is according to 65GeS
2-24.7Ga
2S
3-10CsCl-0.25Er
2S
3-0.05Nd
2S
3The weighing of molar constituent proportioning, after mixing, put into quartz glass tube; The silica tube opening end is inserted vacuum system, extract the water and air in silica tube and the medicine out; When vacuum tightness reaches 10
-2During Pa, utilize oxyhydrogen flame that silica tube is sealed; Silica tube after the sealing is put into and waved stove, begin to wave after being warming up to 900 ℃, and be incubated 12 hours and make it fusion; Then, the silica tube taking-up is also vertically put into the water quenching several seconds, obtain the sulfur-halogen glass block.With sulfur-halogen glass put into resistance furnace in 280 ℃ of annealing to eliminate internal stress.
X-ray diffractogram of powder (Fig. 1) analysis revealed, the sulfur-halogen glass of preparation is typical amorphous structure; The absorption spectrum test result shows, with Er
3+Singly mix sample and compare Nd
3+/ Er
3+Mix sample altogether and have higher pumping efficiency (as shown in Figure 2) at 808nm; Sample utilizes the FSP920 spectrophotometer that is equipped with the OPO laser apparatus to survey infra-red emission in the sample room temperature through surface finish, can be observed centre wavelength at 2.7 microns, corresponding Er
3+:
4I
11/2→
4I
13/2The middle infraluminescence signal of transition.The result shows, Nd
3+/ Er
3+The middle infraluminescence intensity of mixing sample altogether is Er
3+ Singly mix 20 times (as shown in Figure 3) of sample.
Instance 2: with Ge (99.999%), Ga (99.99%), S (99.999%), CsCl (99.9%), Nd
2S
3(99.9%) and Er
2S
3(99.9%) high pure raw material is according to 55GeS
2-34.7Ga
2S
3-10CsCl-0.15Er
2S
3-0.15 Nd
2S
3The weighing of molar constituent proportioning after, put into quartz glass tube; The silica tube opening end is inserted vacuum system, extract the water and air in silica tube and the medicine out; When vacuum tightness reaches 10
-2During Pa, utilize oxyhydrogen flame that silica tube is sealed; Silica tube after the sealing is put into and waved stove, begin to wave after being warming up to 1000 ℃, and be incubated 18 hours and make it fusion; Then, the silica tube taking-up is also vertically put into the water quenching several seconds, obtain the sulfur-halogen glass block.With sulfur-halogen glass put into resistance furnace in 280 ℃ of annealing to eliminate internal stress.Sample utilizes the FSP920 spectrophotometer that is equipped with the OPO laser apparatus to survey infra-red emission in the sample room temperature through surface finish, can be observed centre wavelength at 2.7 microns, corresponding Er
3+:
4I
11/2→
4I
13/2The middle infraluminescence signal of transition.
Instance 3: with Ge (99.999%), Ga (99.99%), S (99.999%), CsCl (99.9%), Nd
2S
3(99.9%) and Er
2S
3(99.9%) high pure raw material is according to 50GeS
2-34.7Ga
2S
3-15CsCl-0.1Er
2S
3-0.2 Nd
2S
3The weighing of molar constituent proportioning after, put into quartz glass tube; The silica tube opening end is inserted vacuum system, extract the water and air in silica tube and the medicine out; When vacuum tightness reaches 10
-2During Pa, utilize oxyhydrogen flame that silica tube is sealed; Silica tube after the sealing is put into and waved stove, begin to wave after being warming up to 950 ℃, and be incubated 24 hours and make it fusion; Then, the silica tube taking-up is also vertically put into the water quenching several seconds, obtain the sulfur-halogen glass block.With sulfur-halogen glass put into resistance furnace in 280 ℃ of annealing to eliminate internal stress.Sample utilizes the FSP920 spectrophotometer that is equipped with the OPO laser apparatus to survey infra-red emission in the sample room temperature through surface finish, can be observed centre wavelength at 2.7 microns, corresponding Er
3+:
4I
11/2→
4I
13/2The middle infraluminescence signal of transition.
Instance 4: with Ge (99.999%), Ga (99.99%), S (99.999%), CsCl (99.9%), Nd
2S
3(99.9%) and Er
2S
3(99.9%) high pure raw material is according to 70GeS
2-24.6Ga
2S
3-5CsCl-0.35Er
2S
3-0.05 Nd
2S
3The weighing of molar constituent proportioning after, put into quartz glass tube; The silica tube opening end is inserted vacuum system, extract the water and air in silica tube and the medicine out; When vacuum tightness reaches 10
-2During Pa, utilize oxyhydrogen flame that silica tube is sealed; Silica tube after the sealing is put into and waved stove, begin to wave after being warming up to 900 ℃, and be incubated 12 hours and make it fusion; Then, the silica tube taking-up is also vertically put into the water quenching several seconds, obtain the sulfur-halogen glass block.With sulfur-halogen glass put into resistance furnace in 280 ℃ of annealing to eliminate internal stress.Sample utilizes the FSP920 spectrophotometer that is equipped with the OPO laser apparatus to survey infra-red emission in the sample room temperature through surface finish, can be observed centre wavelength at 2.7 microns, corresponding Er
3+:
4I
11/2→
4I
13/2The middle infraluminescence signal of transition.
Instance 5: with Ge (99.999%), Ga (99.99%), S (99.999%), CsCl (99.9%), Nd
2S
3(99.9%) and Er
2S
3(99.9%) high pure raw material is according to 55GeS
2-29.4Ga
2S
3-15CsCl-0.5Er
2S
3-0.1 Nd
2S
3The weighing of molar constituent proportioning after, put into quartz glass tube; The silica tube opening end is inserted vacuum system, extract the water and air in silica tube and the medicine out; When vacuum tightness reaches 10
-2During Pa, utilize oxyhydrogen flame that silica tube is sealed; Silica tube after the sealing is put into and waved stove, begin to wave after being warming up to 900 ℃, and be incubated 12 hours and make it fusion; Then, the silica tube taking-up is also vertically put into the water quenching several seconds, obtain the sulfur-halogen glass block.With sulfur-halogen glass put into resistance furnace in 280 ℃ of annealing to eliminate internal stress.Sample utilizes the FSP920 spectrophotometer that is equipped with the OPO laser apparatus to survey infra-red emission in the sample room temperature through surface finish, can be observed centre wavelength at 2.7 microns, corresponding Er
3+:
4I
11/2→
4I
13/2The middle infraluminescence signal of transition.。
Instance 6: with Ge (99.999%), Ga (99.99%), S (99.999%), CsCl (99.9%), Nd
2S
3(99.9%) and Er
2S
3(99.9%) high pure raw material is according to 60GeS
2-34.8Ga
2S
3-5CsCl-0.1Er
2S
3-0.1Nd
2S
3The weighing of molar constituent proportioning after, put into quartz glass tube; The silica tube opening end is inserted vacuum system, extract the water and air in silica tube and the medicine out; When vacuum tightness reaches 10
-2During Pa, utilize oxyhydrogen flame that silica tube is sealed; Silica tube after the sealing is put into and waved stove, begin to wave after being warming up to 900 ℃, and be incubated 12 hours and make it fusion; Then, the silica tube taking-up is also vertically put into the water quenching several seconds, just can obtain the sulfur-halogen glass block.With sulfur-halogen glass put into resistance furnace in 280 ℃ of annealing to eliminate internal stress.Sample utilizes the FSP920 spectrophotometer that is equipped with the OPO laser apparatus to survey infraluminescence in the sample room temperature through surface finish, may detect Er
3+:
4I
11/2→
4I
13/2The middle infraluminescence signal of transition (2.7 microns of centre wavelengths).
Claims (2)
1. infraluminescence sulfur-halogen glass in a kind 2.7 microns, it is characterized in that: the component and the molar content of this transparent glass are following: GeS
2: 50-70mol%; Ga
2S
3: 15-35mol%; CsCl:5-15mol%; Er
2S
3: 0.1-0.5mol%; Nd
2S
3: 0-0.15mol%.
2. the preparation method of the sulfur-halogen glass of a claim 1 comprises the steps:
(1) with the germanium powder, the gallium piece, the sulphur powder, cesium chloride after sulfuration erbium and ncodymium sulfide mix, is transferred in the end mouth of pipe quartz ampoule that sealing by fusing is good, 10
-2Carry out tube sealing with oxyhydrogen flame under the vacuum condition of Pa;
(2) place tubular type to wave stove the good quartz ampoule of step (1) gained sealing-in, be incubated 12～24h down at 900 ℃～1100 ℃, and follow whole process to wave; The quartz ampoule that through water-cooled fusing sample is housed at last obtains sulfur-halogen glass, and will prepared sulfur-halogen glass places under the second-order transition temperature 100 ℃ to anneal with the elimination internal stress.
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|---|---|---|---|
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|---|---|---|---|
| CN201110400933.6A CN102515530B (en) | 2011-12-06 | 2011-12-06 | A kind of mid-infrared luminescence sulfur-halogen glass and technology of preparing thereof |
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| CN102515530B CN102515530B (en) | 2016-09-14 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030300A (en) * | 2013-01-17 | 2013-04-10 | 中国科学院上海光学精密机械研究所 | Erbium and neodymium ion co-doped intermediate infrared 2.7 microns luminous tellurium and sodium based microcrystalline glass |
| CN103382089A (en) * | 2013-07-11 | 2013-11-06 | 中国科学院福建物质结构研究所 | Cs3LaCl6 nanocrystalline-containing transparent chalcohalide glass ceramic and its preparation |
| CN104402195A (en) * | 2014-11-24 | 2015-03-11 | 成都光明光电股份有限公司 | Preparation method for large-sized infrared glass |
| CN109320093A (en) * | 2018-11-16 | 2019-02-12 | 宁波大学 | A kind of transparent microcrystal glass material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2342771A (en) * | 1998-10-13 | 2000-04-19 | Samsung Electronics Co Ltd | Optical Fiber for light amplification |
-
2011
- 2011-12-06 CN CN201110400933.6A patent/CN102515530B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2342771A (en) * | 1998-10-13 | 2000-04-19 | Samsung Electronics Co Ltd | Optical Fiber for light amplification |
Non-Patent Citations (1)
| Title |
|---|
| R.BALDA等: "Upconversion luminescence of transparent Er3+-doped chalcohalide glass-ceramics", 《OPTICAL MATERIALS》, vol. 31, 26 July 2008 (2008-07-26), pages 760 - 764, XP 025962234, DOI: doi:10.1016/j.optmat.2008.06.006 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030300A (en) * | 2013-01-17 | 2013-04-10 | 中国科学院上海光学精密机械研究所 | Erbium and neodymium ion co-doped intermediate infrared 2.7 microns luminous tellurium and sodium based microcrystalline glass |
| CN103382089A (en) * | 2013-07-11 | 2013-11-06 | 中国科学院福建物质结构研究所 | Cs3LaCl6 nanocrystalline-containing transparent chalcohalide glass ceramic and its preparation |
| CN103382089B (en) * | 2013-07-11 | 2018-02-16 | 中国科学院福建物质结构研究所 | Containing Cs3LaCl6Nanocrystalline transparent sulfur-halogen glass ceramics and its preparation |
| CN104402195A (en) * | 2014-11-24 | 2015-03-11 | 成都光明光电股份有限公司 | Preparation method for large-sized infrared glass |
| CN104402195B (en) * | 2014-11-24 | 2018-11-09 | 成都光明光电股份有限公司 | The preparation method of bulk infrared glass |
| CN109320093A (en) * | 2018-11-16 | 2019-02-12 | 宁波大学 | A kind of transparent microcrystal glass material and preparation method thereof |
| CN109320093B (en) * | 2018-11-16 | 2021-08-27 | 宁波大学 | Transparent glass-ceramic material and preparation method thereof |
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|---|---|
| CN102515530B (en) | 2016-09-14 |
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