CN1253121A - Non-linear optical wave guide of thiohelogen glass and its preparing process by ion exchange - Google Patents
Non-linear optical wave guide of thiohelogen glass and its preparing process by ion exchange Download PDFInfo
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- CN1253121A CN1253121A CN 99124023 CN99124023A CN1253121A CN 1253121 A CN1253121 A CN 1253121A CN 99124023 CN99124023 CN 99124023 CN 99124023 A CN99124023 A CN 99124023A CN 1253121 A CN1253121 A CN 1253121A
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- glass
- ion exchange
- preparing process
- optical waveguides
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Abstract
The present invention discloses a non-linear optical wave guide of thiohalogen glass, which uses 3-valence non-linear thiohalogen glass as carrier and is prepared through ion exchange of special fused salt. Its refractivity is 0.001-0.04. Said optical wave guide can be used for high-capacity high-speed transmission of optical signals and as the excellent carrier of integrated optics in microoptical circuit.
Description
The invention belongs to technical field of inorganic material, relating to a kind of is the optical waveguides of carrier with the unorganic glass, relates in particular to a kind of sulfur-halogen glass and is optical waveguides of carrier and preparation method thereof with the sulfur-halogen glass.
Optical waveguides is a large amount of optical signals carriers of transmission fast, also is the matrix of integrated optics in the micro-optic circuit, and optical waveguides is in opticfiber communication, and integrated optics has important use and is worth in variable refractivity optics and the sensory field of optic fibre.Along with optical communication, photometry is calculated, the development of optical information processing, the information processing device of Full-optical more and more cause people's research interest, as: optically controlled optical switch, the optical bistability device, optical logic gate, image intensifer, wavelength division multiplexer, optical fiber lasers etc., wherein many devices are constructed on the non-linear optical waveguide basis.Can expect, next stage the photon technology based on photonic device will have very strong competition potential, wherein nonlinear light guide wave device and technology will play a significant role undoubtedly.
Optical waveguides is carrier with the nonlinear optical material, and therefore, the quality of nonlinear optical material will directly influence the performance of optical waveguides.Nonlinear optical material generally is divided into three kinds of crystalline material, glass material and macromolecular materials, generally can adopt following formula to weigh the quality of material:
W=κ
0Δ n '/α
0In the τ formula:
W----nonlinear optical material factor of merit
κ
0----scale-up factor
α
0----linear absorption coefficient
τ-------time of response
Δ n '----nonlinear refractive index changes
As can be seen, the raising of full optical device quality factor must make nonlinear refractive index changes delta n ' increase, linear absorption coefficient α simultaneously from formula (1)
0Reduction and time of response reduce and could realize.
At present, most non-linear optical waveguides all adopt semiconductor material, and the band gap resonance optical nonlinearity of semiconductor material is very strong, causes bigger Δ n '.This is very unfavorable for the semiconductor material that is operated in band gap resonance, if avoid resonance region, then can cause nonlinear decline;
When adopting organic polymer material and glass material to be carrier, then can avoid absorption peak, the main drawback of organic polymer material is that light injury threshold is lower, awaits further solution;
Glass material, especially chalcogenide halide glass (abbreviation sulfur-halogen glass) has then overcome the shortcoming of above-mentioned many materials, has high third-order non-linear coefficient simultaneously, short time of response and low loss, in addition, glass property is stable, sees through wide ranges, is easy to processing, cost is low, be the excellent material of preparation non-linear optical waveguide,, attract much attention more and more as emerging nonlinear material.And present glass optical waveguide mainly is to be that the fused salt of basic glass and nitrate carries out ion-exchange and is prepared with oxide glass, and the nonlinear factor of oxide glass is lower, thereby is mainly used in the linear optics preparation of devices.
In sum, should research and develop a kind of unorganic glass with high trivalent nonlinear factor as early as possible is the non-linear optical waveguide of carrier, with the needs of the information technology that satisfies develop rapidly.
One of purpose of the present invention is to provide a kind of sulfur-halogen glass with high trivalent nonlinear factor;
It is the non-linear optical waveguide of carrier that two of purpose of the present invention is to provide a kind of sulfur-halogen glass with high trivalent nonlinear factor;
Three of purpose of the present invention is to disclose that a kind of to adopt special fused salt be the method for the non-linear optical waveguide of carrier by ion-exchange preparation with the sulfur-halogen glass.
Design of the present invention is such:
Discover, the nonlinear factor of chalcogenide glass is much larger than common oxide glasses and fluoride glass, it is the excellent material of preparation non-linear optical waveguide, but because the scope that sees through of most of chalcogenide glass is only in 2-20 μ m, and general communication window is near 0.98,1.31 and 1.55 μ m, so chalcogenide glass is difficult to directly as the non-linear optical waveguide material.The loss of fluoride glass is minimum, but its poor chemical stability, is subjected to the erosion of environment easily and influences serviceability.The present invention adds halogenide in chalcogenide glass, make it to form a kind of novel sulfur-halogen glass system--GeS
2-Ga
2S
3-Y (Y be among KCl, KBr, KI, AgBr or the AgI a kind of) is owing to after having added halogenide, make this glass have the principal advantages of chalcogenide glass and halide glass, and suppressed the weakness of the two to a certain extent.Said glass not only has broad transparency range (0.42～11.5 μ m), the better physical chemical property, and contain monovalent metallic ion, make it to become the excellent material that can prepare non-linear optical waveguide by ion-exchange.
According to above-mentioned design, the present invention proposes following technical scheme:
The chemical structure of the said non-linear sulfur-halogen glass of the present invention is as follows:
GeS
2-Ga
2S
3-Y
Wherein:
Y is a kind of among KCl, KBr, KI, AgBr or the AgI;
Its ratio of components is:
GeS
2-Ga
2S
3 70％～90％
Y 30％～10％
It more than is molar percentage.
The transparency range of said glass is quite wide, comprises visible light and infrared two zones (0.42-11.5 μ m), and transmitance is up to (thickness 3mm) more than 80%, loss is low, n ' is up to 2.0-2.5 for the nonlinear refractive index changes delta, and non-linear effect is obvious, and nonlinear polarization coefficient χ is 10
-11-10
-12In the esu scope, physicochemical property are good, are a kind of good non-linear optical waveguide materials.
Traditional quartz ampoule vacuum-sealing high temperature (950-110 ℃) scorification is adopted in founding of glass, and this is a kind of method of routine, all is described in many patents and document, and the present invention repeats no more.Cl, Br and I can be selected from KCl, KBr or KI respectively; Ag can be selected from AgBr or AgI respectively.
Above-mentioned sulfur-halogen glass can be used to prepare non-linear optical waveguide.
Said optical waveguides is a carrier with above-mentioned sulfur-halogen glass, and its effective diffusion coefficient is 0.05 * 10
-10Cm
2S
-1～700 * 10
-10Cm
2S
-1, refractive indices n is 0.001-0.04, the exchange degree of depth is 1 μ m～1000 μ m.
Said optical waveguides also is preparation like this:
Above-mentioned sulfur-halogen glass is placed interchanger, carry out ion exchange reaction with organic molten salt under the protection of rare gas element, said organic molten salt is for having the monovalent base metallic cation, as Na
+, K
+, Ag
+, Cs
+, Rb
+Deng organic salt such as in Citrate trianion, stearate, oleate or the palmitate etc. one or more, positively charged ion in the said organic salt and the Ag in the glass or K carry out Na respectively
+-K
+, Na
+-Ag
+, K
+-Ag
+, Cs
+-K
+, Rb
+-K
+, Rb
+-Ag
+, Cs
+-Ag
+Carry out ion-exchange, obtain said non-linear optical waveguide.
Be 1 hour-80 hours swap time, and temperature is 210 ℃-310 ℃, and temperature is too high, will cause the structure of glass inside loose, and the refringence that produces owing to ion-exchange is disappeared; The too low spread coefficient of ion-exchange that then can make of temperature is too little, and makes ion exchange reaction be difficult to carry out.Therefore, preferred temperature is 230 ℃～290 ℃.
By regulating the may command exchange swap time degree of depth, the exchange degree of depth can reach 8-1200 μ m, and refractive indices n is between 0.001-0.04.Also can carry out secondary ions exchanges and prepares the buried type optical waveguides.
The great advantage of optical waveguides of the present invention is that cost is low, and technology is simple, and the non-linear phenomena of optical waveguides is obvious, easy with the optical fiber coupling, light wave sees through wide ranges, and the optical waveguide applications scope is wide, is the excellent carrier of integrated optics in quick transmission of a kind of a large amount of optical signal and the micro-optic circuit.
To be further described related content of the present invention by embodiment below, but embodiment does not limit protection scope of the present invention.
Embodiment 1
With diameter is 12mm, and thickness is the 50GeS of 4mm
2-25Ga
2S
3-25AgI glass and 100ml potassium oleate fused salt place interchanger, under 270 ℃ of nitrogen protections, carry out K
+-Ag
+Ion-exchange, be 30 hours swap time, the K that obtains
+The ion-exchange degree of depth is 256 μ m, and effective diffusion coefficient is 60.7 * 10
-10Cm
2S
-1, refractive indices n is 0.02.
Embodiment 2
With diameter is 12mm, and thickness is the 60GeS of 4mm
2-20Ga
2S
3-20AgI glass and 100ml Tripotassium Citrate fused salt place interchanger, under 270 ℃ of nitrogen protections, carry out K
+-Ag
+Ion-exchange, be 10 hours swap time, the K that obtains
+The ion-exchange degree of depth is 205 μ m, and refractive indices n is 0.01.
Embodiment 3
With diameter is 12mm, and thickness is the 50GeS of 4mm
2-40Ga
2S
3-10KI glass and 100ml oleic acid caesium fused salt place interchanger, under 270 ℃ of nitrogen protections, carry out Cs
+-Kg
+Ion-exchange, be 30 hours swap time, the Cs that obtains
+The ion-exchange degree of depth is 9 μ m, and refractive indices n is 0.03.
Embodiment 4
With diameter is 12mm, and thickness is the 50GeS of 4mm
2-25Ga
2S
3The fused salt mixt of-25KI glass and potassium oleate and oleic acid caesium (1: 1, weight ratio) places interchanger, in the environment of 270 ℃ of nitrogen protections, carries out Cs
+-Kg
+Ion-exchange, be 30 hours swap time, the Cs that obtains
+The ion-exchange degree of depth is 8 μ m, and refractive indices n is 0.02.
Claims (8)
1. non-linear sulfur-halogen glass is characterized in that having general structure as follows:
GeS
2-Ga
2S
3-Y
Wherein:
Y is a kind of among KCl, KBr, KI, AgBr or the AgI;
Its ratio of components is:
GeS
2-Ga
2S
3 70％～90％
Y 30％～10％
It more than is molar percentage.
2. non-linear optical wave guide of thiohelogen glass, it is characterized in that: be carrier with the sulfur-halogen glass, refractive indices n is 0.001-0.04, and the general structure of said sulfur-halogen glass is as follows:
GeS
2-Ga
2S
3-Y
Wherein:
Y is a kind of among KCl, KBr, KI, AgBr or the AgI;
Its ratio of components is:
GeS
2-Ga
2S
3 70％～90％
Y 30％～10％
It more than is molar percentage.
3. the preparing process by ion exchange of optical waveguides as claimed in claim 2 places interchanger with said sulfur-halogen glass, carries out ion exchange reaction with organic molten salt under the protection of rare gas element, obtains said non-linear optical waveguide, it is characterized in that:
Said organic molten salt is the organic salt with monovalent base metallic cation;
Be 1 hour～80 hours swap time;
Temperature is 210 ℃-310 ℃.
4. the preparing process by ion exchange of optical waveguides as claimed in claim 3 is characterized in that:
Said organic salt is Na
+, K
+, Ag
+, Cs
+, Rb
+Organic salt.
5. the preparing process by ion exchange of optical waveguides as claimed in claim 4, it is characterized in that: said organic salt is Na
+, K
+, Ag
+, Cs
+, Rb
+Citrate trianion, stearate, oleate or palmitate in one or more.
6. the preparing process by ion exchange of optical waveguides as claimed in claim 3 is characterized in that preferred temperature is 230 ℃～290 ℃.
7. the preparing process by ion exchange of optical waveguides as claimed in claim 5 is characterized in that preferred temperature is 230 ℃～290 ℃.
8. the preparing process by ion exchange of optical waveguides as claimed in claim 6 is characterized in that preferred temperature is 230 ℃～290 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99124023A CN1128113C (en) | 1999-11-18 | 1999-11-18 | Non-linear optical wave guide of thiohelogen glass and its preparing process by ion exchange |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99124023A CN1128113C (en) | 1999-11-18 | 1999-11-18 | Non-linear optical wave guide of thiohelogen glass and its preparing process by ion exchange |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1253121A true CN1253121A (en) | 2000-05-17 |
| CN1128113C CN1128113C (en) | 2003-11-19 |
Family
ID=5283120
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99124023A Expired - Fee Related CN1128113C (en) | 1999-11-18 | 1999-11-18 | Non-linear optical wave guide of thiohelogen glass and its preparing process by ion exchange |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1128113C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100375727C (en) * | 2006-01-24 | 2008-03-19 | 武汉理工大学 | Sulfur halogen glass and its production for superfast light switch |
| CN101907739A (en) * | 2010-07-30 | 2010-12-08 | 西南科技大学 | Additional electric field-assisted ion exchange device |
| CN101244891B (en) * | 2008-03-11 | 2011-03-16 | 武汉理工大学 | Preparation of environment-friendly infrared frequency multiplication sulfureous series vitro-ceramic |
| CN101255010B (en) * | 2008-01-10 | 2012-07-04 | 武汉理工大学 | Chalcohalide glasses ceramic having broadband optical window and preparation method thereof |
| CN102936095A (en) * | 2012-11-06 | 2013-02-20 | 华东理工大学 | Preparation of silver ion doped transparent glass with high ionic conductivity |
| RU2781425C1 (en) * | 2022-04-06 | 2022-10-11 | Федеральное государственное бюджетное учреждение науки Институт химии высокочистых веществ им. Г.Г.Девятых Российской академии наук | Method for producing highly pure chalcogenide glasses containing silver iodide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1135726A1 (en) * | 1983-06-17 | 1985-01-23 | ЛГУ им.А.А.Жданова | Chalgogenide glass having ion conductivity |
| SU1402913A1 (en) * | 1986-12-03 | 1988-06-15 | ЛГУ им.А.А.Жданова | Composition of membrane of chalcogenid glass electrode for determining sodium ions |
| US5392376A (en) * | 1994-04-11 | 1995-02-21 | Corning Incorporated | Gallium sulfide glasses |
-
1999
- 1999-11-18 CN CN99124023A patent/CN1128113C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100375727C (en) * | 2006-01-24 | 2008-03-19 | 武汉理工大学 | Sulfur halogen glass and its production for superfast light switch |
| CN101255010B (en) * | 2008-01-10 | 2012-07-04 | 武汉理工大学 | Chalcohalide glasses ceramic having broadband optical window and preparation method thereof |
| CN101244891B (en) * | 2008-03-11 | 2011-03-16 | 武汉理工大学 | Preparation of environment-friendly infrared frequency multiplication sulfureous series vitro-ceramic |
| CN101907739A (en) * | 2010-07-30 | 2010-12-08 | 西南科技大学 | Additional electric field-assisted ion exchange device |
| CN102936095A (en) * | 2012-11-06 | 2013-02-20 | 华东理工大学 | Preparation of silver ion doped transparent glass with high ionic conductivity |
| RU2781425C1 (en) * | 2022-04-06 | 2022-10-11 | Федеральное государственное бюджетное учреждение науки Институт химии высокочистых веществ им. Г.Г.Девятых Российской академии наук | Method for producing highly pure chalcogenide glasses containing silver iodide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1128113C (en) | 2003-11-19 |
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