CN103979792A

CN103979792A - Gold-doped chalcogenide glass and preparation method thereof

Info

Publication number: CN103979792A
Application number: CN201410169895.1A
Authority: CN
Inventors: 张芳芳; 陈飞飞; 于秋爽; 戴世勋; 许银生
Original assignee: Ningbo University
Current assignee: Ningbo University
Priority date: 2014-04-25
Filing date: 2014-04-25
Publication date: 2014-08-13
Anticipated expiration: 2034-04-25
Also published as: CN103979792B

Abstract

The present invention discloses gold-doped chalcogenide glass, which has a composition formula of (100-w)GaxGeySz.wAu, wherein x is 0-47, y is 3-66, z is 20-75, w is 0.5-10, and x, y, z and w are mole fractions. According to the present invention, Au is introduced into the Ga-Ge-S chalcogenide glass, and under the premise of no change of the main advantage of the Ga-Ge-S chalcogenide glass, the high ionic polarizability of Au is utilized to increase the nonlinear refractive index of the glass to the 10<-17> m<2>/w magnitude order and concurrently increase the stability of the physicochemical properties of the Ga-Ge-S chalcogenide glass, such that the application range of the Ga-Ge-S chalcogenide glass is expanded.

Description

Chalcogenide glass of a kind of gold doping and preparation method thereof

Technical field

The present invention relates to a kind of chalcogenide glass material, especially relate to chalcogenide glass of a kind of gold doping and preparation method thereof.

Background technology

Ga-Ge-S glass is a kind of chalcogenide glass that had not only had visible light permeability but also had infrared light perviousness.This glass system is using S as network the structural groups of negative ions, be a kind of become glass ability and the strongest chalcogenide glass of anti-crystallization ability, it becomes glass ability between oxide glass and seleno chalcogenide glass.

But the optical nonlinearity of Ga-Ge-S glass is lower, according to the report of Marchese, the high non-linearity refractive index n under Ga-Ge-S glass 800nm wavelength ₂only can reach 3 × 10 ^-18m ²/ W." the high non-linearity GeS that U.S.'s " chemical physics wall bulletin " publishes ₂– Ga ₂s ₃– CdS chalcogenide glass and its super fast response time " (X.F.Wang, Z.W.Wang, J.G.Yu, C.L.Liu, X.J.Zhao, and Q.H.Gong, " Large and ultrafast third-order optical nonlinearity of GeS ₂-Ga ₂s ₃-CdSchalcogenide glass, " Chem.Phys.Lett.399,230-233 (2004) .) adds Cd in Ga-Ge-S glass ²⁺ion increases its nonlinear refractive index, makes it reach 3.5 × 10 ^-18m ²/ W." the Ge – Ga – S – PbI that " solid state chemistry journal " published ₂chalcogenide glass three rank and second nonlinear " (H.Guo, H.Tao, S.Gu, X.Zheng, Y.Zhai, S.Chu, X.Zhao, S.Wang, and Q.Gong, " Third-and second-order optical nonlinearity of Ga-Ge-S-PbI ₂chalcohalide glasses, in " J.Solid State Chem.180,240-248 (2007) .), report adds Pb in Ga-Ge-S glass ²⁺ion can increase the n of glass ₂value, makes it reach 7.5 × 10 ^-18m ²/ W.Visible, the n of existing Ga-Ge-S glass ₂value is substantially 10 ^-18m ²the order of magnitude of/W, at the same order of magnitude, has limited its use with partial oxide glass.

Summary of the invention

Technical problem to be solved by this invention is: for the deficiencies in the prior art, provide chalcogenide glass of a kind of gold doping and preparation method thereof, under the prerequisite of optical property that ensures Ga-Ge-S glass excellence, improved its nonlinear refractive index.

The present invention solves the problems of the technologies described above adopted technical scheme: a kind of chalcogenide glass of gold doping, its composition formula is (100-w) Ga _xge _ys _zwAu, wherein x=0～47, y=3～66, z=20～75, w=0.5～10, x, y, z, w are molar fraction.

Preferably, x=5～35 in described composition formula, y=10～45, z=30～70, w=0.5～10.

Preferably, x=10 in described composition formula, y=25, z=65, w=0.5～10.

The preparation method of the chalcogenide glass of above-mentioned gold doping, comprises the following steps:

1) raw material is prepared: be ready to various raw materials and mix according to proportioning raw materials, and mixed raw material is packaged in to vacuum tightness is 10 ^-4in encloses container below Pa;

2) high-temperature fusion and quenching: heating encloses container, the mixing raw material of encapsulation is carried out to high-temperature fusion, Heating temperature is 850～1200 DEG C, be 16～48h heat-up time; After finishing, heating by the distilled water of 0～40 DEG C of encloses container immersion, the melts encapsulating in encloses container being carried out to quenching, obtains work in-process glass;

3) annealing and cooling: encloses container is annealed together with work in-process glass, and annealing temperature is 320～450 DEG C, and annealing time is 1～5h; After annealing finishes, encloses container is down to room temperature together with work in-process glass with the rate of temperature fall of 1～10 DEG C/h, opens encloses container and obtain the Ga-Ge-S glass that gold adulterates.

Compared with prior art, the invention has the advantages that: the present invention is incorporated into Au in Ga-Ge-S chalcogenide glass, utilize the macroion polarizability of Au to make the nonlinear refractive index n of glass ₂value is increased to 10 ^-17m ²the order of magnitude of/W, can expand the range of application of Ga-Ge-S chalcogenide glass; The main advantage of Ga-Ge-S chalcogenide glass is visible light permeability, is introducing after Au, and its optical band gap Eopg rangeability is very little, and the ability of its saturating visible ray is unaffected; And Au is different from his inert metals such as Ag, the atomic radius of Au is larger, can form positive monovalent ion (Au in glass ⁺) and positive trivalent ion (Au ³⁺), Au ³⁺can become key with multiple S, form comparatively stable network structure, be conducive to improve the stability of Ga-Ge-S chalcogenide glass physicochemical property.

Embodiment

Below in conjunction with embodiment, the present invention is described in further detail.

The preparation method of the chalcogenide glass of the gold doping of each embodiment comprises the following steps:

1) raw material is prepared: be ready to various raw materials and mix according to the proportioning raw materials of embodiment and comparative example respectively, and mixed raw material is packaged in respectively to vacuum tightness is 10 ^-4in quartz ampere bottle below Pa, the raw material of embodiment 1～5 and comparative example and proportioning are in table 1;

2) high-temperature fusion and quenching: heating quartz ampere bottle, the mixing raw material of encapsulation is carried out to high-temperature fusion, Heating temperature is 950 DEG C, be 24h heat-up time; After finishing, heating by the distilled water of 25 DEG C of quartz ampere bottle immersions, the melts encapsulating in quartz ampere bottle being carried out to quenching, obtains work in-process glass;

3) annealing and cooling: quartz ampere bottle is annealed together with work in-process glass, and annealing temperature is 380 DEG C, and annealing time is 2h; After annealing finishes, quartz ampere bottle is down to room temperature together with work in-process glass with the rate of temperature fall of 5 DEG C/h, opens quartz ampere bottle, take out the Ga-Ge-S glass of gold doping, detect its performance.The performance of embodiment 1～5 and comparative example is in table 1.

The raw material of table 1 embodiment 1～5 and comparative example and proportioning, performance

As seen from Table 1, in Ga-Ge-S chalcogenide glass, introduce after Au its nonlinear refractive index n ₂value is increased to (1.2～1.6) × 10 ^-17m ²/ W, optical band gap Eopg rangeability is very little, and therefore the present invention is not changing under the prerequisite of Ga-Ge-S chalcogenide glass major advantage, and its nonlinear refractive index has been improved to an order of magnitude, has improved the stability of Ga-Ge-S chalcogenide glass physicochemical property simultaneously.

Claims

1. a chalcogenide glass for gold doping, is characterized in that, its composition formula is (100-w) Ga _xge _ys _zwAu, wherein x=0 ~ 47, y=3 ~ 66, z=20 ~ 75, w=0.5 ~ 10, x, y, z, w are molar fraction.

2. the chalcogenide glass of a kind of gold doping according to claim 1, is characterized in that x=5 ~ 35 in described composition formula, y=10 ~ 45, z=30 ~ 70, w=0.5 ~ 10.

3. the chalcogenide glass of a kind of gold doping according to claim 1, is characterized in that x=10 in described composition formula, y=25, z=65, w=0.5 ~ 10.

4. a preparation method for the chalcogenide glass of the doping of the gold described in claim 1 or 2 or 3, is characterized in that comprising the following steps:

2) high-temperature fusion and quenching: heating encloses container, the mixing raw material of encapsulation is carried out to high-temperature fusion, Heating temperature is 850 ~ 1200 DEG C, be 16 ~ 48h heat-up time; After finishing, heating by the distilled water of 0 ~ 40 DEG C of encloses container immersion, the melts encapsulating in encloses container being carried out to quenching, obtains work in-process glass;

3) annealing and cooling: encloses container is annealed together with work in-process glass, and annealing temperature is 320 ~ 450 DEG C, and annealing time is 1 ~ 5h; After annealing finishes, encloses container is down to room temperature together with work in-process glass with the rate of temperature fall of 1 ~ 10 DEG C/h, opens encloses container and obtain the Ga-Ge-S glass that gold adulterates.