CN108793737A - A kind of chalcogenide glass and preparation method thereof - Google Patents
A kind of chalcogenide glass and preparation method thereof Download PDFInfo
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- CN108793737A CN108793737A CN201810859238.8A CN201810859238A CN108793737A CN 108793737 A CN108793737 A CN 108793737A CN 201810859238 A CN201810859238 A CN 201810859238A CN 108793737 A CN108793737 A CN 108793737A
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- chalcogenide glass
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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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
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Abstract
The invention belongs to chalcogenide glass fields, and it discloses a kind of chalcogenide glass, the chalcogenide glass is Ge-Sb-Se chalcogenide glass；The chalcogenide glass average coordination number is 2.35-2.45.The object of the present invention is to provide a kind of chalcogenide glass, which has ideal brittleness index, refractive index and structural stability, while the invention also discloses preparation methods.
Description
Technical field
The present invention relates to chalcogenide glass fields, and in particular to a kind of chalcogenide glass and preparation method thereof.
Background technology
Chalcogenide glass be a kind of one or more and glass formation element silicon by chalcogen sulphur, selenium, tellurium, germanium, phosphorus,
Arsenic, the covalent key compound of the formation such as antimony, with the larger density, linear refractive index that weaker key is strong, high, high non-linear
Specific refractivity and ultrafast response time (femtosecond to subpicosecond magnitude), optics depend on material composition through range, can
Far infrared region (20 μm) is expanded to from visible (600nm), therefore is a kind of important material in infrared optics, in Military Application
(such as infrared tracking, interference, the navigation of search target and optical remote sensing detection) and civil field (such as atmospheric monitoring, infrared light
Spectroscopy, environmental protection and biologic medical etc.) all have a wide range of applications.
Commercialization chalcogenide glass product generally has six kinds, including As2Se3 present on international at present, domestic market,
Ge33As12Se55, Ge10As40Se50, Ge28Sb12Se60, Ge22As20Se58, Ge20Sb15Se65, due to glass material
The essence of covalent bond, there are larger structural relaxations for material itself, this causes the optical device based on these materials, and there is tight
The service life of weight is used for a long time and may be set due to the unstable reduction for causing properties of product of this body structure of material
New Glasses Materials of the meter manufacture with minimal structure relaxation have great importance.
When sulphur based material is used for optical waveguide, the form that chalcogenide glass is prepared into flat film is needed, it is such thin
Film is typically that block materials are resolved into the state of molecule, ion or cluster under vacuum conditions and then are agglomerated on substrate again
It forms.The film prepared in this way by decomposition-coacervation process under thermodynamics nonequilibrium condition due to carrying out, with block
Body material compares, and film includes a large amount of defect key, and structural relaxation is compared bulk and become apparent, therefore for flat film wave
It leads, with greater need for the optical material for using stable structure.
An important parameter is the brittleness index (fragility index) of glass in glass material, it is defined as,
More than glass transformation temperature, viscosity increases the speed of variation with temperature, is a kind of good for evaluating glass structure stability
Bad index.The big material of brittleness index means that the temperature change of the above very little of glass transformation temperature may all lead to non-crystal mesh
The rapid collapse of network structure, therefore the glass of smaller brittleness index has smaller structural relaxation and ideal chalcogenide glass
Material.
Invention content
The object of the present invention is to provide a kind of chalcogenide glass, the chalcogenide glass have ideal brittleness index, refractive index with
And structural stability, while the invention also discloses preparation methods.
The concrete scheme of the present invention is as follows：A kind of chalcogenide glass, the chalcogenide glass are Ge-Sb-Se chalcogenide glass；Institute
The chalcogenide glass average coordination number stated is 2.35-2.45.
In above-mentioned chalcogenide glass, in the chalcogenide glass, it is made of following molar constituent：Ge：12.5-17.5；
Sb：10-12.5；Se：72.5-77.5.
In above-mentioned chalcogenide glass, in the chalcogenide glass, it is made of following molar constituent：Ge：15；Sb：10；
Se：75.
Meanwhile the invention also discloses a kind of preparation method of chalcogenide glass as described above, including the following steps：
1) raw material preparation：Ge, Sb, Se raw material are weighed according to the raw material proportioning calculated and is uniformly mixed, and will be after mixing
Raw material be packaged in vacuum degree be 10-5In Torr closed high purity quartz containers below；
2) high-temperature fusion and quenching：Closed container is heated, high-temperature fusion is carried out to the mixed raw material of encapsulation, heating temperature is
850~950 DEG C, heating time be 12~for 24 hours；After heating with high wind room temperature to the fusant that is encapsulated in closed container into
Row quenching obtains the chalcogenide glass of semi-finished product；
3) it anneals and cooling：Closed container is placed in together with semi-finished product chalcogenide glass in thermal annealing stove and is annealed, is annealed
Temperature is 200-220 DEG C, and annealing time is 3~5h；After annealing by closed container together with Semi-finished glass with 1~10
DEG C/rate of temperature fall of h is slowly at the uniform velocity down to room temperature, it opens closed quartz container and obtains Ge-Sb-Se ternary chalcogenide glass.
Beneficial effects of the present invention are：
The brittleness index of typical ternary chalcogenide glass is 28 or so, especially compared with other different glass ingredients in same system
It is existing commercialization ternary chalcogenide glass component, the brittleness index of the new glass component proposed in the present invention is obviously reduced；
With such material thermal evaporation or sputtering sedimentation, the optical thin film of stable structure can be obtained.
Description of the drawings
Fig. 1 is the optical performance test result for the film that 1-4 of the embodiment of the present invention and comparative example 1-2 are prepared.
Specific implementation mode
With reference to embodiment, the invention will be further described, but does not constitute any limitation of the invention, any
In the modification for the limited number of time that scope of the invention as claimed is made, still in scope of the presently claimed invention.
The preparation method of Ge-Sb-Se chalcogenide glass：
Include the following steps：
1) raw material preparation：Various raw materials have been weighed according to the raw material proportioning of embodiment and comparative example and be uniformly mixed respectively,
And it is 10 that mixed raw material is packaged in vacuum degree respectively-5In Torr quartzy ampere bottles below, Examples 1 to 4 and comparison
The raw material and proportioning of example are shown in Table 1；
2) high-temperature fusion and quenching：Heated quartz ampere bottle carries out high-temperature fusion, heating temperature to the mixed raw material of encapsulation
It it is 850 DEG C, heating time is for 24 hours；By quartzy ampere bottle high wind or ice water to quartzy ampere bottle and interior encapsulation after heating
Fusant carries out quenching, obtains semi-finished product chalcogenide glass；
3) it anneals and cooling：Quartzy ampere bottle is placed in together with Semi-finished glass in thermal annealing stove and is annealed, annealing temperature
Degree is 200-220 DEG C, annealing time 3h；After annealing by quartzy ampere bottle together with Semi-finished glass with 5 DEG C/h's
Rate of temperature fall is down to room temperature, opens quartzy ampere bottle, takes out chalcogenide glass, and test its performance.
With reference to the above method, chalcogenide glass is prepared according to the formula of the following table 1, and tested, test is implemented
Example 1-4 and comparative example 1-2's as a result, as follows：
The performance parameter of the chalcogenide glass of 1 different ratio of table
After above-mentioned formula is applied to thin-film material, the film refractive index variation under its illumination condition, result are tested
Such as Fig. 1.Abscissa is light fluence, unit kJ/cm in figure2；Ordinate is refraction of the thin-film material in 1.5 mu m wavebands
Rate.
The preparation method of thin-film material is：Using the GeSbSe glass of preparation as evaporation material, using thermal evaporation or sputtering
Mode prepare corresponding film under vacuum conditions.
From figure one as it can be seen that two kinds of materials of comparative example are with the increase of illumination flux, variation is apparent, illustrates these material structures
Stability is bad；In comparison, four kinds of materials of the present embodiment, refractive index have almost no change or vary less, illustrate
The present invention greatly reduces the brittleness index of material, to subtract under the premise of no change Ge-Se chalcogenide glass major advantages
The small structural relaxation of material, considerably increases the structural stability of material, then can stabilizing device significantly for waveguiding structure
Performance parameter, prolong the service life.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (4)
1. a kind of chalcogenide glass, which is characterized in that the chalcogenide glass is Ge-Sb-Se chalcogenide glass；The chalcogenide glass
Average coordination number is 2.35-2.45.
2. chalcogenide glass according to claim 1, which is characterized in that in the chalcogenide glass, by following molar constituent
Composition：Ge：12.5-17.5；Sb：10-12.5；Se：72.5-77.5.
3. chalcogenide glass according to claim 3, which is characterized in that in the chalcogenide glass, by following molar constituent
Composition：Ge：15；Sb：10；Se：75.
4. a kind of preparation method of chalcogenide glass as described in claim 1-3 is arbitrary, which is characterized in that include the following steps：
1) raw material preparation：Ge, Sb, Se raw material are weighed according to the raw material proportioning that calculates and is uniformly mixed, and by mixed original
It is 10 that material, which is packaged in vacuum degree,-5In Torr closed high purity quartz containers below；
2) high-temperature fusion and quenching：Closed container is heated, high-temperature fusion, heating temperature 850 are carried out to the mixed raw material of encapsulation
~950 DEG C, heating time be 12~for 24 hours；The fusant encapsulated in closed container is carried out in room temperature with high wind after heating
Quenching obtains the chalcogenide glass of semi-finished product；
3) it anneals and cooling：Closed container is placed in together with semi-finished product chalcogenide glass in thermal annealing stove and is annealed, annealing temperature
It it is 200-220 DEG C, annealing time is 3~5h；After annealing by closed container together with Semi-finished glass with 1~10 DEG C/h
Rate of temperature fall be slowly at the uniform velocity down to room temperature, open closed container and obtain Ge-Sb-Se ternary chalcogenide glass.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810859238.8A CN108793737A (en) | 2018-07-31 | 2018-07-31 | A kind of chalcogenide glass and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810859238.8A CN108793737A (en) | 2018-07-31 | 2018-07-31 | A kind of chalcogenide glass and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502970A (en) * | 2018-12-25 | 2019-03-22 | 南通瑞森光学股份有限公司 | A kind of infrared long wave leads to glass and its preparation process |
| CN116594088A (en) * | 2023-03-29 | 2023-08-15 | 暨南大学 | Infrared light field regulating device and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232161A (en) * | 2013-05-03 | 2013-08-07 | 中国建筑材料科学研究总院 | Preparation method and equipment of Ge-Sb-Se systematic infrared glass |
| CN104843996A (en) * | 2015-04-23 | 2015-08-19 | 宁波鼎创红外精密光学科技有限公司 | Environmentally friendly low-dispersion chalcogenide glass and preparation method thereof |
| CN107417097A (en) * | 2017-05-09 | 2017-12-01 | 武汉理工大学 | A kind of preparation method of high-fracture toughness chalcogenide glass |
-
2018
- 2018-07-31 CN CN201810859238.8A patent/CN108793737A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232161A (en) * | 2013-05-03 | 2013-08-07 | 中国建筑材料科学研究总院 | Preparation method and equipment of Ge-Sb-Se systematic infrared glass |
| CN104843996A (en) * | 2015-04-23 | 2015-08-19 | 宁波鼎创红外精密光学科技有限公司 | Environmentally friendly low-dispersion chalcogenide glass and preparation method thereof |
| CN107417097A (en) * | 2017-05-09 | 2017-12-01 | 武汉理工大学 | A kind of preparation method of high-fracture toughness chalcogenide glass |
Non-Patent Citations (1)
| Title |
|---|
| 魏文猴: "Ge-Sb-Se硫系玻璃的制备、结构及性能研究", 《中国博士学位论文全文数据库（工程科技Ⅰ辑）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109502970A (en) * | 2018-12-25 | 2019-03-22 | 南通瑞森光学股份有限公司 | A kind of infrared long wave leads to glass and its preparation process |
| CN116594088A (en) * | 2023-03-29 | 2023-08-15 | 暨南大学 | Infrared light field regulating device and preparation method thereof |
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Application publication date: 20181113 |