CN102167515A - Conductive infrared frequency-doubling sulfur neoceramic glass and preparation method thereof - Google Patents
Conductive infrared frequency-doubling sulfur neoceramic glass and preparation method thereof Download PDFInfo
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- CN102167515A CN102167515A CN2011100083852A CN201110008385A CN102167515A CN 102167515 A CN102167515 A CN 102167515A CN 2011100083852 A CN2011100083852 A CN 2011100083852A CN 201110008385 A CN201110008385 A CN 201110008385A CN 102167515 A CN102167515 A CN 102167515A
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- 239000011521 glass Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 8
- 239000011593 sulfur Substances 0.000 title abstract 3
- 239000000126 substance Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 230000009021 linear effect Effects 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 6
- 239000004038 photonic crystal Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002360 explosive Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 3
- 239000010453 quartz Substances 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- 239000005387 chalcogenide glass Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000000146 host glass Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910021489 α-quartz Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/32—Non-oxide glass compositions, e.g. binary or ternary halides, sulfides or nitrides of germanium, selenium or tellurium
- C03C3/321—Chalcogenide glasses, e.g. containing S, Se, Te
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/04—Fibre optics, e.g. core and clad fibre compositions
- C03C13/041—Non-oxide glass compositions
- C03C13/043—Chalcogenide glass compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/10—Compositions for glass with special properties for infrared transmitting glass
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention relates to a conductive infrared frequency-doubling sulfur neoceramic glass and a preparation method thereof. The neoceramic glass is prepared from the following simple substances: 10-16mol% of Ge, 20-23mol% of Ga, 56-62mol% of S and 2.2-13.3mol% of Li. The preparation method of the neoceramic glass comprises the following steps: proportioning; putting the weighed simple substances in a quartz tube, vacuumizing, and sealing by using oxyhydrogen flame; putting in a rocking furnace, and heating at a heating rate of 0.5-3 DEG C/min, so that each simple substance fully reacts with sulfur; heating from room temperature to 120 DEG C, and preserving the temperature for 1-5 hours; continuing to heat to 900-1000 DEG C, and preserving the constant temperature for 1-24 hours; and quenching at 800-900 DEG C for 1-24 hours, thus separating out nonlinear microlite which is the neoceramic glass. The invention has the advantages of low production cost, excellent performance of the prepared product, wide application range and the like.
Description
Technical field
The present invention relates to the photoelectric functional field of new, be specifically related to infrared frequency multiplication sulfureous microcrystalline glass in series of a kind of conductivity type and preparation method thereof.
Background technology
Nonlinear optical material is one of critical material of optical information technology, has wide practical use at aspects such as full optical signal processing, photonic computers.Glass is a kind of nonlinear optical material, compare with oxide glass, sulphur system's (halogen) glass is because its strong covalent linkage characteristic and the characteristics that have a large amount of textural defect, and be easier to obtain high nonlinear optical coefficients, in the Electro-optical Modulation field of infrared spectral region great prospect.
GeS
2-Ga
2S
3-CdS, GeS
2-Ga
2S
3The optical property of sulphur such as-AgCl system and sulfur-halogen glass system all had detailed research, had obtained frequency-doubled effect preferably under outer field action, and the generation of its frequency-doubled effect mainly depends on outer field action changes the structure of glass.GeS
2-Ga
2S
3-Li
2Contain some as β-GeS in the S system
2, Li
2Ga
2GeS
6And LiGaS
2Deng the composition of non-linear optic crystal, will separate out such non-linear optic crystal at glass by certain heat treated, thereby make glass directly produce non-linear effect, aspect optical property, get a good eye value.While GeS
2-Ga
2S
3-Li
2S chalcogenide glass system since the Li ionic exist, thereby make glass have electroconductibility.
LiBC
2(B=In, Ga; C=S, Se, Te) crystal is owing to its good nonlinear optics has obtained extensive studies.This crystalloid has the scope that sees through of broad, very high laser damage threshold and bigger Clock Multiplier Factor, wherein LiGaS
2The scope that sees through be 0.33-12 μ m; d
31=5.8pm/V, d
33=10.7pm/V compares AgGaS
2Crystal is low; But its laser damage threshold can reach 4.15eV, much larger than AgGaS
22.75eV.Iowa State University has synthesized Li recently
2Ga
2GeS
6Crystal, experiment draws d
Eff=16pm/V compares AgGaS
2Crystalline d
36=19pm/V is lower slightly, but its laser damage threshold can reach 3.65eV, signal is still very stable under long lasing, so this is a kind of very promising non-linear optic crystal, and weak point is can't obtain at present the monocrystalline of large-size.
Just because of GeS
2-Ga
2S
3-Li
2Contain some as β-GeS in the S system
2, Li
2Ga
2GeS
6And LiGaS
2Deng the non-linear optic crystal advantage, the second-order nonlinear optical property of the devitrified glass that expectation will make behind this chalcogenide glass crystallization will be very excellent, because Li
2S is to problems such as the one-tenth glass scope of the burn into research cost of container, this system are narrower, and the optical property that contains sulphur system (halogen) glass of lithium never obtains careful research.
Summary of the invention
Technical problem to be solved by this invention is: in view of the existing in prior technology shortcoming and defect, a kind of infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type with excellent second nonlinear performance is provided, the easy preparation of this devitrified glass and the method for safety in production are provided simultaneously.
The present invention solves its technical problem and adopts following technical scheme:
The infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type provided by the invention (abbreviation devitrified glass), it is made by following simple substance raw material:
Ge: 10 ~ 16; Ga:20 ~ 23; S:56 ~ 62; Li:2.2 ~ 13.3 are mol%.
The infrared frequency multiplication sulfureous microcrystalline glass in series of above-mentioned conductivity type provided by the invention, it is as the preparation material of all-optical switch or photonic crystal fiber etc.
The infrared frequency multiplication sulfureous microcrystalline glass in series of above-mentioned conductivity type provided by the invention, its preparation method may further comprise the steps:
(1) batching: take by weighing the simple substance raw material by following proportioning, be mol%,
Ge?：10~16；?Ga：20~23；S：56~62；?Li：2.2~13.3；
(2) the simple substance raw material that takes by weighing is put into silica tube, vacuumize, use the oxyhydrogen flame sealing-in;
(3) put into and wave stove, heat up, each simple substance raw material and sulphur are fully reacted according to 0.5 ~ 3 ℃/min of temperature rise rate;
When (4) being warming up to 120 ℃, be incubated 1 ~ 5 hour by room temperature;
(5) continue to heat up, when being warming up to 900 ~ 1000 ℃, constant temperature 1 ~ 24 hour;
(6) quenched 1 ~ 24 hour at 800 ~ 900 ℃, separate out non-linear crystallite, it is a conductivity type infrared frequency multiplication devitrified glass.
During batching, in the vacuum operating case, take by weighing the simple substance raw material.And note, when taking by weighing the simple substance lithium, will avoid ingress of air because lithium can with airborne N
2, O
2Deng reacting.
In the step (4), when elemental sulfur 120 ℃ change liquid into after can and Li vigorous reaction takes place, generate two kinds of product Li
2S and Li
2S
n, reaction equation is respectively:
2Li+ S → Li
2S, S are liquid,
2Li+nS→Li
2S
n，n=2~4，
Wherein: Li
2S
nBe a kind of explosive substance, therefore will be incubated 1 ~ 5 hour to avoid blast at 120 ℃.
In the step (5), when being warming up to 400～800 ℃, need control temperature rise rate, be controlled at 1 ℃/min as far as possible, can't stand Li because violent intensification can make Glass tubing hold
2The corrosion of S; After 800 ℃, control temperature rise rate for being less than or equal to 0.5 ℃/min as far as possible.
The infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type of the present invention's preparation, it is as the preparation material of all-optical switch or photonic crystal fiber.
The present invention compared with prior art has following major advantage:
One. production cost is low: overcome external high price chemical reagent Li
2The dependence of S directly utilizes active lithium simple substance to prepare the infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type, has both prevented effectively that reaction from generating Li
2S easily blasts, and also provides cost savings simultaneously.
They are two years old. excellent performance: because GeS
2-Ga
2S
3-Li
2Contain β-GeS in the S system
2, Li
2Ga
2GeS
6And LiGaS
2Deng the second-order non-linear optical crystal advantage, can obtain to separate out the devitrified glass that Clock Multiplier Factor is very big, physical and chemical performance is stable.Simultaneously because GeS
2-Ga
2S
3-Li
2The Li ionic exists in the S system, makes devitrified glass have electroconductibility.
They are three years old. use wide: not only can be used for the optics chalcogenide glass of synthetic Containing Sulfur lithium, also can be used for the synthesizing lithium ion conductive glass.
Description of drawings
Fig. 1 is the infrared frequency multiplication sulfureous microcrystalline glass in series (56.5GeS of conductivity type of the present invention
2-37.5Ga
2S
3-6Li
2S) through the second harmonic intensity of the devitrified glass of 380 ℃ of thermal treatments 7 and 8 hours, 400 ℃ thermal treatment preparation in 10 hours.
Fig. 2 is the infrared frequency multiplication sulfureous microcrystalline glass in series (40GeS of conductivity type of the present invention
2-41Ga
2S
3-19Li
2S) through the second harmonic intensity of the devitrified glass of 420 ℃ of thermal treatments 6 ~ 9 hours preparation.
Fig. 3 is the infrared frequency multiplication sulfureous microcrystalline glass in series (37.5GeS of conductivity type of the present invention
2-37.5Ga
2S
3-25Li
2S) through 425 ℃ of respectively thermal treatments 6 hours, the second harmonic intensity of 8 hours and the devitrified glass that prepared in 10 hours.
Fig. 4 is the temperature increasing schedule curve of the infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type of the present invention.
Embodiment
The invention provides a kind of is raw material with Li, Ge, Ga, S simple substance directly, and preparation can be used for infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type of usefulness such as all-optical switch or photonic crystal fiber and preparation method thereof.
The invention will be further described below in conjunction with specific embodiment, but do not limit the present invention.
Embodiment 1:
Conductivity type infrared frequency multiplication devitrified glass is made by following simple substance raw material:
Ge: 10 ~ 16; Ga:20 ~ 23; S:56 ~ 62; Li:2.2 ~ 13.3 are mol%.
Embodiment 2: the preparation of conductivity type infrared frequency multiplication devitrified glass
(1) batching: take by weighing the simple substance raw material by following proportioning, be mol%,
Ge?：10~16；?Ga：20~23；S：56~62；?Li：2.2~13.3；
(2) the simple substance raw material that takes by weighing is put into silica tube, vacuumize, use the oxyhydrogen flame sealing-in;
(3) put into and wave stove, heat up, each simple substance raw material and sulphur are fully reacted according to 0.5 ~ 3 ℃/min of temperature rise rate;
When (4) being warming up to 120 ℃, be incubated 1 ~ 5 hour by room temperature;
(5) continue to heat up, when being warming up to 900 ~ 1000 ℃, constant temperature 1 ~ 24 hour;
(6) quenched 1 ~ 24 hour at 800 ~ 900 ℃, separate out non-linear crystallite, it is a conductivity type infrared frequency multiplication devitrified glass.
Embodiment 3: the preparation of conductivity type infrared frequency multiplication devitrified glass
1) weighing 1.35gGe, 1.33gGa, 2.255gS, 0.062gLi in the vacuum operating case put into silica tube, vacuumize, and use the oxyhydrogen flame sealing-in;
2) put into and wave stove, be warming up to 120 ℃, begin to wave and, simple substance lithium and sulphur are fully reacted this temperature insulation 1 hour with the temperature rise rate of 2 ℃/min;
3) with the temperature rise rate about 1.5 ℃/min temperature is risen to 400 ℃, be incubated 1 hour;
4) temperature rise rate with 1 ℃/min rises to 750 ℃ with temperature;
5) with the temperature rise rate about 0.5 ℃/min temperature is risen to 950 ℃, be incubated after 10 hours 850 ℃ of taking-ups, shrend, 360 ℃ of annealing obtained homogeneous glass in 5 hours;
6) dsc analysis gets Tg at 422 ℃; The transmitance that sees through the spectroscopic analysis host glass is 70 ~ 80%.
7), obtain containing the devitrified glass 40GeS of nonlinear optics crystallite 420 ℃ of difference thermal treatment 5 ~ 10 hours
2-41Ga
2S
3-19Li
2S, it is a conductivity type infrared frequency multiplication devitrified glass.Crystalline structure and Li through this devitrified glass of XRD test expression
2Ga
2GeS
6Identical.
Embodiment 4: the preparation of conductivity type infrared frequency multiplication devitrified glass
1) weighing 1.48gGe, 0.948gGa, 1.995gS, 0.015gLi in the vacuum operating case put into silica tube, vacuumize, and use the oxyhydrogen flame sealing-in;
2) put into and wave stove, be warming up to 120 ℃ with the temperature rise rate of 2 ℃/min, and, simple substance lithium and sulphur fully reacted this temperature insulation 1 hour;
3) with the temperature rise rate about 1.5 ℃/min temperature is risen to 400 ℃, be incubated 1 hour;
4) temperature rise rate with 1 ℃/min rises to 750 ℃ with temperature, begins to wave;
5) with the temperature rise rate about 0.5 ℃/min temperature is risen to 950 ℃ then, be incubated after 10 hours and take out shrend, annealing, obtain homogeneous glass at 850 ℃.
6) dsc analysis gets Tg about 418 ℃; Seeing through the transmitance of spectroscopic analysis glass before thermal treatment is 70 ~ 80%.
7) respectively at 390 ℃, 400 ℃ thermal treatment 5h and 10h, 380 ℃ of thermal treatment 5 ~ 10h obtain containing the devitrified glass 56.5GeS of nonlinear optics crystallite
2-37.5Ga
2S
3-6Li
2S, it is a conductivity type infrared frequency multiplication devitrified glass.With the second harmonic intensity maximum of Maker the Schlieren method test, be about 6% times (as Fig. 1) of alpha-quartz at 400 ℃ of thermal treatment 10h and 380 ℃ of thermal treatment 7h, 8h.
8) the XRD test result shows, the conductivity type infrared frequency multiplication devitrified glass 56.5GeS that this example obtains
2-37.5Ga
2S
3-6Li
2The contained microcrystal of S mainly is a sulfur-gallium compound, comprises GaS and Ga
2S
3, and with Ga
2S
3Be main.
Embodiment 5: the preparation of conductivity type infrared frequency multiplication devitrified glass
1) weighing 1.35gGe, 1.33gGa, 2.255gS, 0.062gLi in the vacuum operating case put into silica tube, vacuumize, and use the oxyhydrogen flame sealing-in;
2) put into and wave stove, be warming up to 120 ℃, begin to wave and, simple substance lithium and sulphur are fully reacted this temperature insulation 1 hour with the temperature rise rate of 2 ℃/min;
3) with the temperature rise rate about 1.5 ℃/min temperature is risen to 400 ℃, be incubated 1 hour;
4) temperature rise rate with 1 ℃/min rises to 750 ℃ with temperature;
5) with the temperature rise rate about 0.5 ℃/min temperature is risen to 950 ℃, be incubated after 10 hours 850 ℃ of taking-ups, shrend, 360 ℃ of annealing obtained homogeneous glass in 5 hours;
6) dsc analysis gets Tg at 422 ℃; The transmitance that sees through the spectroscopic analysis host glass is 70 ~ 80%.
7), obtain containing the devitrified glass 40GeS of nonlinear optics crystallite 420 ℃ of difference thermal treatment 5 ~ 10 hours
2-41Ga
2S
3-19Li
2S, it is a conductivity type infrared frequency multiplication devitrified glass.Crystalline structure and Li through this devitrified glass of XRD test expression
2Ga
2GeS
6Identical.
The 40GeS of embodiment 5 preparations
2-41Ga
2S
3-19Li
2S component glass is behind 420 ℃ of thermal treatment 9h, and the Maker striped is the bag shape of rule, though the transmitance of 532nm has only 0.33%, second harmonic intensity has reached 34%(such as Fig. 2 of alpha-quartz)
Embodiment 6: the preparation of conductivity type infrared frequency multiplication devitrified glass
1) weighing 1.345gGe, 1.28gGa, 2.29gS, 0.085gLi in the vacuum operating case put into silica tube, vacuumize, and use the oxyhydrogen flame sealing-in;
2) put into and wave stove, be warming up to 120 ℃, begin to wave and, simple substance lithium and sulphur are fully reacted this temperature insulation 1 hour with the temperature rise rate of 2 ℃/min;
3) with the temperature rise rate about 1.5 ℃/min temperature is risen to 400 ℃, be incubated 1 hour;
4) temperature rise rate with 1 ℃/min rises to 750 ℃ with temperature;
5) with the temperature rise rate about 0.5 ℃/min temperature is risen to 960 ℃, be incubated after 10 hours 850 ℃ of taking-ups, shrend, 350 ℃ of annealing obtained homogeneous glass in 5 hours;
6) dsc analysis gets Tg at 431 ℃; The transmitance that sees through the spectroscopic analysis host glass is 70 ~ 80%.
7), obtain containing the devitrified glass 37.5GeS of nonlinear optics crystallite 425 ℃ of difference thermal treatment 6,8,10 hours
2-37.5Ga
2S
3-25Li
2S, it is a conductivity type infrared frequency multiplication devitrified glass.Crystalline structure and Li through this devitrified glass of XRD test expression
2Ga
2GeS
6Identical.
The 37.5GeS of embodiment 6 preparations
2-37.5Ga
2S
3-25Li
2S component glass is behind 425 ℃ of thermal treatment 10h, and the Maker striped is the bag shape of rule, and second harmonic intensity has reached 55%(such as Fig. 3 of alpha-quartz).
Embodiment 7: the application of the infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type
The infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type is as the preparation material of all-optical switch.
Embodiment 8: the application of the infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type
The infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type is as the preparation material of photonic crystal fiber.
Claims (8)
1. infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type is characterized in that being made by following simple substance raw material:
Ge: 10 ~ 16; Ga:20 ~ 23; S:56 ~ 62; Li:2.2 ~ 13.3 are mol%.
2. the purposes of the infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type is characterized in that the preparation material of the infrared frequency multiplication sulfureous microcrystalline glass in series of the described conductivity type of claim 1 as all-optical switch or photonic crystal fiber etc.
3. the preparation method of the infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type is characterized in that adopting the method that may further comprise the steps:
(1) batching: take by weighing the simple substance raw material by following proportioning, be mol%,
Ge?：10~16；?Ga：20~23；S：56~62；?Li：2.2~13.3；
(2) the simple substance raw material that takes by weighing is put into silica tube, vacuumize, use the oxyhydrogen flame sealing-in;
(3) put into and wave stove, heat up, each simple substance raw material and sulphur are fully reacted according to 0.5 ~ 3 ℃/min of temperature rise rate;
When (4) being warming up to 120 ℃, be incubated 1 ~ 5 hour by room temperature;
(5) continue to heat up, when being warming up to 900 ~ 1000 ℃, constant temperature 1 ~ 24 hour;
(6) quenched 1 ~ 24 hour at 800 ~ 900 ℃, separate out non-linear crystallite, it is a conductivity type infrared frequency multiplication devitrified glass.
4. preparation method according to claim 3 is characterized in that taking by weighing the simple substance raw material in the vacuum operating case.
5. preparation method according to claim 4 is characterized in that will avoiding ingress of air when taking by weighing the simple substance lithium.
6. preparation method according to claim 3 is characterized in that: in the step (4), when elemental sulfur 120 ℃ change liquid into after can and Li vigorous reaction takes place, generate two kinds of product Li
2S and Li
2S
n, reaction equation is respectively:
2Li+ S → Li
2S, S are liquid,
2Li+nS→Li
2S
n，n=2~4，
Wherein: Li
2S
nIt is a kind of explosive substance.
7. preparation method according to claim 3 is characterized in that: in the step (5), need control temperature rise rate when being warming up to 400～800 ℃, be controlled at 1 ℃/min as far as possible; After 800 ℃, control temperature rise rate for being less than or equal to 0.5 ℃/min as far as possible.
8. the infrared frequency multiplication sulfureous microcrystalline glass in series of conductivity type of the described method of arbitrary claim preparation in the claim 3 to 7, it is as the preparation material of all-optical switch or photonic crystal fiber.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162429A (en) * | 2017-07-17 | 2017-09-15 | 宁波大学 | A kind of infrared chalcogenide glass ceramic of graded index and preparation method thereof |
| CN107394263A (en) * | 2017-06-29 | 2017-11-24 | 深圳大学 | A kind of sulphide crystallites glass of high-lithium ion content and preparation method thereof |
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2011
- 2011-01-17 CN CN2011100083852A patent/CN102167515B/en not_active Expired - Fee Related
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| Title |
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| 《Solid State Ionics》 19961231 M. YAMASHITA等 Thin-film preparation of the li2S-GeS2-Ga2S3 glass system by sputtering 摘要，表1试样1 1 第89卷, * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107394263A (en) * | 2017-06-29 | 2017-11-24 | 深圳大学 | A kind of sulphide crystallites glass of high-lithium ion content and preparation method thereof |
| CN107394263B (en) * | 2017-06-29 | 2019-09-27 | 深圳大学 | A kind of sulphide crystallites glass of high-lithium ion content and preparation method thereof |
| CN107162429A (en) * | 2017-07-17 | 2017-09-15 | 宁波大学 | A kind of infrared chalcogenide glass ceramic of graded index and preparation method thereof |
| CN107162429B (en) * | 2017-07-17 | 2019-10-08 | 宁波大学 | A kind of infrared chalcogenide glass ceramic of graded index and preparation method thereof |
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