CN1253394C - Chalcogenide glass containing rare earth elements and method for preparing same - Google Patents
Chalcogenide glass containing rare earth elements and method for preparing same Download PDFInfo
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- CN1253394C CN1253394C CN 03141532 CN03141532A CN1253394C CN 1253394 C CN1253394 C CN 1253394C CN 03141532 CN03141532 CN 03141532 CN 03141532 A CN03141532 A CN 03141532A CN 1253394 C CN1253394 C CN 1253394C
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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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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention discloses novel gadolinium-containing sulfide glass for the fields of infrared optics, optical electronics, etc., and a preparation method thereof. The present invention is one kind of sulfide glass which is prepared by using sulfur, germanium and arsenic as main components and introducing a rare earth element Gd. The preparation method of the sulfide glass comprises the steps of glass batch preparing, vacuum sealing, glass melting, etc. After being treated through surface grinding and polishing, the obtained glass makes the tests of an infrared spectrum, microhardness, density, DSC, XRD, etc. Results show that the rare earth element Gd has large solubility in the glass of the system. Compared with the glass of the existing Ge-S and Ge-As-S system, the gadolinium-containing sulfide glass reserves the original infrared transmittance, has the characteristics of red shift generation through the penetration of an infrared cut-off wavelength, obvious improvement of heat and mechanical property. In addition, Because gadolinium has a high negative electrode electric potential, the gadolinium is an optimal oxygen eliminating agent.
Description
Technical field
The present invention relates to a kind of chalcogenide glass and preparation method thereof, specifically, relate to a kind of chalcogenide glass that contains rare earth element and preparation method thereof.
Background technology
Nonoxide glass is one of research focus in the present material science, and its impellent is the demands of fields such as optics, photoelectronics, semiconductor science to novel material.Wherein, chalcogenide glass has many interesting aspects, and for example, they have bigger quality and more weak bond energy; Their energy gap is little than oxide glass, is generally 1～3eV, belongs to semi-conductor; They can be with the preparation of traditional melt quenching method, can both form glass usually in the stoichiometry of a broad or nonstoichiometric composition scope, therefore has the continuously adjustable characteristics of performance.Because above-mentioned these characteristics, chalcogenide glass obtains practical application in many aspects as infrared, photoelectron, semiconductor material etc.In recent years because optical amplifier and optical fiber laser are successful at coml, exploitation by the rare earth ion doped effective infrared lumious material of chalcogenide glass conduct causes people's extensive interest and concern, this is because chalcogenide glass has low phonon energy and high refractive index, therefore having lower multi-phonon and go to swash rate and higher absorption/stimulated emission cross section, is the infraluminescence substrate material more better than oxide glass.
Rare-earth element gadolinium has bigger solubleness in the oxide glass system, its introducing amount is different because of system, reaches as high as more than the 15mol%.But gadolinium-doped is not appeared in the newspapers so far as yet in chalcogenide glass.Can predict according to the structural similarity principle, might improve other rare earth luminous atom content of introducing to contain the gadolinium chalcogenide glass because of the rare earth atom position of being introduced in the glass network structure as substrate material, thereby improve the luminous efficiency of doping chalcogenide glass.Introduce the phonon energy that the bigger gadolinium atom of ordination number also helps further reduction system, make the IR-cut wavelength to the displacement of long wave direction.In addition, induce the micritization of generation to make heat, mechanical property the best of glass by high field intensity, high coordination gadolinium, and saturating infrared property is unaffected, the higher negative potential current potential of gadolinium then makes it have stronger deoxygenation ability.
Summary of the invention
The object of the invention is, provide a kind of can be applied to fields such as infrared optics (especially as saturating infrared optical element of the 3rd atmospheric window 8～12 μ m), the photoelectronics rear-earth-doped substrate material of active infrared optical element (especially as) contain gadolinium chalcogenide glass and preparation method thereof.
Inventive concept:
Chalcogenide glass is the class in the traditional chalcogenide glass, is characterized in the energy gap broad, in visible or near-infrared region certain perviousness is arranged, and is suitable to different rare earth luminous ionic substrate materials.Rare-earth element gadolinium (Gd) has bigger atomic mass, helps reducing the phonon energy of system; Because the similarity of rare earth ion structure is that substrate material helps improving rare earth luminous ionic dissolving power to contain the gadolinium chalcogenide glass; Owing to the high field intensity of rare earth ion and compact structureization and the micritization effect that high coordination characteristic is produced, help improving heat, the mechanical property of glass.In addition, because gadolinium has higher negative potential current potential, be a kind of preferable oxygen scavenger therefore.
Technical scheme:
The present invention introduces rare-earth element gadolinium (Gd) and a class new sulfide compounds glass of formation.The design of the composition of this system glass has taken into account the high optical transmission, long infrared by wavelength and better heat, mechanical property of formation ability, the near-infrared region of glass.
The said chalcogenide glass that contains gadolinium of the present invention comprises following component and content (content is in atomic percent):
S 50～65％
Ge 20～45％
Gd 0.1～10％
As 0～20％
Visible and the near infrared absorption notch of above-mentioned glass is long to be 800nm, infraredly surpass 12 μ m by wavelength, transition temperature can reach more than 330 ℃, microhardness can reach more than the 2000MPa, compare with the Ge-As-S system glass with existing Ge-S, the said gadolinium chalcogenide glass that contains of the present invention also possesses the IR-cut wavelength and produces red shift, characteristics such as heat, the remarkable improvement of mechanical property except that keeping original infrared transmittivity.In addition, because gadolinium has higher negative potential current potential, be a kind of preferable oxygen scavenger therefore, make original oxygenate impurity absorption peak disappear or weaken.
Preparing the said method that contains the gadolinium chalcogenide glass of the present invention comprises the steps:
A) preparation of glass batch:
To adopt simple substance S, Ge, As and Gd be raw material by said ratio mixed glass batch, wherein the purity of S, Ge, As is preferably greater than 99.999%, Gd purity is preferably 99.9%;
B) vacuum seal:
To place quartz ampoule by step a) gained glass batch, under vacuum state, the sealing-in quartz ampoule;
Wherein: used quartz ampoule preferably adopts the method for acid soak and heat to carry out pre-treatment in advance, and preferred acid solution is 50% (V/V) hydrofluoric acid or hydrochloric acid, the vacuum tightness during sealing-in in the ampoule preferred 10
-2Pa.
C) glass smelting:
To found 8～10 hours postcooling by the good quartz ampoule of step b) sealing-in at 900 ℃～1000 ℃, place retort furnace then,, promptly get the said gadolinium chalcogenide glass that contains of the present invention after the cooling 200 ℃ of insulation half an hour;
Wherein: quartz ampoule preferably is in dynamically in the process of founding, so that it is abundant with the glass metal homogenizing that glass batch is reacted completely.
For making thermal property the best of obtained glass, saturating infrared property is unaffected, the XRD spectrum does not show the crystallization peak, can carry out micritization to it and handle (thermal treatment), it is that cooled glass specimen is reentered into retort furnace that micritization is handled key step, at 150 ℃～300 ℃, be incubated and cool to room temperature with the furnace after 2～6 hours and get final product.
Embodiment
Below will the invention will be further described by embodiment, but the cited case does not limit protection domain of the present invention:
Embodiment 1
Formulating of recipe:
Adopt sulphur, germanium, gadolinium three-part system.Design of components is as follows:
The glass of table 1 embodiment 1 is formed (at%)
| S | Ge | Gd |
| 60 | 37 | 3 |
The admixtion preparation:
Adopting high purity (＞99.999%) elemental sulfur, germanium and purity respectively is that 99.9% simple substance gadolinium is a raw material, carries out formula calculation and admixtion preparation by the composition shown in the table 2.Admixtion places the quartz ampoule of handling, vacuum (10
-2Pa) sealing-in.
Glass smelting:
The glass that fusing is good cools off in air together with quartz ampoule.Cooled quartz ampoule is directly moved in the retort furnace.Retort furnace is warming up to 200 ℃ in advance.Insulation after half an hour is closed electric furnace in retort furnace, and glass specimen cools to room temperature with the furnace.
Thermal treatment:
Cooled glass specimen is reentered into retort furnace, is heated to through preferred determined temperature and insulation.Heating temperature is 180 ℃, and soaking time is 3 hours.Insulation after finishing is closed retort furnace, and glass specimen cools to room temperature with the furnace.Separate out the gadolinium sulfide nanocrystal after the thermal treatment in the glass.Show as heat, performance the best of glass, saturating infrared property is unaffected, and the XRD spectrum does not show the crystallization peak.
Test-results:
Resulting glass specimen is done following performance measurement after surface grinding, polished finish.The results are shown in Table 2.
The The performance test results of table 2 embodiment 1 glass
| Shortwave absorbs limit (μ m) | IR-cut wavelength (μ m) | Density (g/cm 3) | Molecular volume (cm 3/mo1) | Transition temperature (℃) | Microhardness (MPa) |
| 0.8 | 12.50 | 3.301 | 15.38 | 345 | 2560 |
Embodiment 2～6
In each of the embodiments described below, the preparation method of glass is with embodiment 1, and the different glass that is adopted is formed and the performance test result lists in table 3 and table 4 respectively.
The glass of table 3 embodiment 2～6 is formed (at%)
| Sequence number | S | Ge | As | Gd |
| 2 | 58 | 35 | 0 | 7 |
| 3 | 67 | 32 | 0 | 1 |
| 4 | 58 | 35 | 3 | 4 |
| 5 | 60 | 33 | 5 | 2 |
| 6 | 66 | 31 | 2 | 1 |
The performance test result of table 4 embodiment 2～5 glass
| Numbering | Density (g/cm 3) | Molecular volume (cm 3/mol) | Microhardness H v(MPa) | Transition temperature T g(℃) |
| 2 | 3.391 | 14.02 | 2072 | 315 |
| 3 | 2.937 | 15.75 | 2316 | 335 |
| 4 | 3.256 | 16.13 | 2162 | 320 |
| 5 | 3.143 | 15.93 | 2335 | 330 |
| 6 | 3.020 | 15.47 | 2250 | 310 |
Claims (5)
1, a kind of chalcogenide glass that contains gadolinium, it comprises following component and content:
S 50～65％
Ge 20～45％
Gd 0.1～10％
As 0～20％
Wherein: content is in atomic percent.
2, prepare the method for the described glass of claim 1, it is characterized in that, said preparation method comprises the steps:
A) adopting simple substance S, Ge, As and Gd is that raw material is by the mixed glass batch that gets of the described proportioning of claim 1;
B) will place quartz ampoule by step a) gained glass batch, under vacuum state, the sealing-in quartz ampoule;
C) will found 8～10 hours postcooling by the good quartz ampoule of step b) sealing-in at 900 ℃～1000 ℃, place retort furnace then,, promptly get the said gadolinium chalcogenide glass that contains of the present invention after the cooling 200 ℃ of insulation half an hour.
3, preparation method as claimed in claim 2 is characterized in that, wherein the vacuum tightness in the ampoule is 10 during sealing-in
-2Pa.
As claim 2 or 3 described preparation methods, it is characterized in that 4, wherein used quartz ampoule adopts the acid soak method to carry out pre-treatment.
5, preparation method as claimed in claim 4 is characterized in that, wherein said acid solution is 50V/V% hydrofluoric acid or hydrochloric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141532 CN1253394C (en) | 2003-07-11 | 2003-07-11 | Chalcogenide glass containing rare earth elements and method for preparing same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03141532 CN1253394C (en) | 2003-07-11 | 2003-07-11 | Chalcogenide glass containing rare earth elements and method for preparing same |
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| Publication Number | Publication Date |
|---|---|
| CN1569709A CN1569709A (en) | 2005-01-26 |
| CN1253394C true CN1253394C (en) | 2006-04-26 |
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| CN 03141532 Expired - Fee Related CN1253394C (en) | 2003-07-11 | 2003-07-11 | Chalcogenide glass containing rare earth elements and method for preparing same |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2698340C1 (en) * | 2018-12-24 | 2019-08-26 | Федеральное государственное бюджетное учреждение науки Институт химии высокочистых веществ им. Г.Г.Девятых Российской академии наук | Method of producing extremely pure chalcogenide glass |
| CN111204973A (en) * | 2020-01-08 | 2020-05-29 | 中山大学 | Preparation method of high-quality rare earth doped chalcogenide film |
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Assignee: Perfect Energy Technology (Shanghai) Co., Ltd. Assignor: East China University of Science and Technology Contract fulfillment period: 2008.8.1 to 2014.7.31 contract change Contract record no.: 2008310000214 Denomination of invention: Chalcogenide glass containing rare earth elements and method for preparing same Granted publication date: 20060426 License type: General permission Record date: 20081114 |
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Free format text: COMMON LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.8.1 TO 2014.7.31; CHANGE OF CONTRACT Name of requester: ZHANGFENG ENERGY TECHNOLOGY (SHANGHAI) CO., LTD. Effective date: 20081114 |
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Granted publication date: 20060426 Termination date: 20100711 |