CN1821132A - Sulfer-halogen glass having high second-order non-linear polarizability and its heat polarizing method - Google Patents
Sulfer-halogen glass having high second-order non-linear polarizability and its heat polarizing method Download PDFInfo
- Publication number
- CN1821132A CN1821132A CN 200610024737 CN200610024737A CN1821132A CN 1821132 A CN1821132 A CN 1821132A CN 200610024737 CN200610024737 CN 200610024737 CN 200610024737 A CN200610024737 A CN 200610024737A CN 1821132 A CN1821132 A CN 1821132A
- Authority
- CN
- China
- Prior art keywords
- glass
- sample
- sulfur
- halogen
- halogen glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Glass Compositions (AREA)
Abstract
The present invention discloses a kind of sulfur halide glass with high second order non-linear polarizability and its heat polarizing method. The sulfur halide glass has the composition of (70-x)GeS2-(15+x/2)Ga2S3-(15+x/2)RH. During the cooling of the sulfur halide glass, the polarizing voltage is raised constantly so as to obtain second order non-linear polarizability up to 5.7 pm/V, and the high second order non-linear polarizability may exist for long time in room temperature condition. The glass of the present invention is one frequency doubling and photoelectronic modulating material with excellent developing latent.
Description
Technical field
The present invention relates to can be used for preparing frequency doubling device, electric light opens the light and electro-optical modulation device etc. has glass of second harmonic generating effect and preparation method thereof.
Background technology
Glass structure has macroscopic symmetry, so its even order nonlinear optical coefficients are zero in theory.As everyone knows, can destroy the macroscopic symmetry of glass structure effectively, thereby produce second order nonlinear optical effect by thermoaeization method.Generally speaking, thermoaeization promptly at first is heated to sample pre-set temperature, applies high DC electric field then and is incubated for some time, treats subsequently to remove applying direct current electric field again after sample is cooled to room temperature gradually.In traditional thermoaeization method, applying direct current electric field to the beginning all keeps steady state value extremely eventually.
Based on the distinctive various fine qualities of glass, cheap as cost of manufacture, be easy to processing, physical and chemical performance stable, can be directly and optical fiber and optical waveguides be complementary etc., the various countries scientific research personnel has all launched a large amount of research to the glass nonlinear optics, yet research mainly concentrates on third-order non-linear and various oxide glass.The research data of report shows in the recent period, and sulfur-halogen glass is because have bigger quality, so its third-order nonlinear optical coefficient χ is obviously greater than silica glass and other various nonoxide glasses; To have a more weak key strong because of sulfur-halogen glass again, exists a large amount of defectives in its structure, be easy to polarized, so prediction can produce tangible second harmonic generating effect in sulfur-halogen glass.
Simultaneously sulfur-halogen glass also have concurrently good infrared transmission performance, high linearity and nonlinear refractive index, can be directly and optical fiber and optical waveguides advantage such as be coupled, thereby sulfur-halogen glass is regarded as a kind of frequency multiplication novel, that have development potentiality and photoelectricity is modulated material.Generally speaking, we are difficult to the high glass sample of alkali metal content is carried out effective thermoaeization, this is because this type of glass often has very high specific conductivity, thereby is difficult in the inner space built in field that keeps a kind of stable existence of glass sample after hyperpolarization is handled.This has just limited with the glass with second order nonlinear optical effect to a great extent is matrix, adopts ion exchange method to prepare the possibility of optical waveguides.
Summary of the invention
One of technical issues that need to address of the present invention provide a kind of sulfur-halogen glass that can prepare frequency doubling device and ion exchange optical waveguide.
Two of the technical issues that need to address of the present invention are to be disclosed in the thermoaeization method that induces the second harmonic generating effect in the above-mentioned sulfur-halogen glass.
The present invention has developed the sulfur-halogen glass with good infrared transmission performance and high nonlinear second-order optical susceptibility.In the sulfur-halogen glass sample, induced the second harmonic generating effect by special thermoaeization method.We have also studied thermoaeization method to the optics of glass sample and the influence of thermomechanical property simultaneously.
The main component of the glass that the present invention relates to is elemental Germanium (Ge), gallium (Ga), sulphur (S) and alkali metal halide (RH) etc., and founding of sulfur-halogen glass sample adopted traditional melt quenching method.
The glass that the present invention relates to consists of:
(70-x)GeS
2-(15+x/2)Ga
2S
3-(15+x/2)RH
Wherein: x=0～20, R=Na or K; H=Cl or Br;
The thermoaeization method that induces the second harmonic generating effect in the above-mentioned sulfur-halogen glass comprises the steps:
The glass sample of above-mentioned composition is placed between two stainless steel electrodes, between upper/lower electrode and sample surfaces, place the commercial silica glass thin slice that thickness is 0.05～0.2mm simultaneously, fixing;
Be heated to the high-voltage dc of 150～200 ℃ of after-applied 0.5～0.8kv, be incubated 10～30 minutes, stop heating, cooled off 1～10 minute, sample is taken out, and while boosted voltage to 0.6～0.9kv is after cooling off 10～30 minutes under 10～35 ℃ the environment, boosted voltage to 0.91～1.0kv cooled off 10～30 minutes once more, promptly obtained glass of the present invention.
The present invention adopts a kind of special thermoaeization method, promptly in the sample process of cooling, improve constantly polarizing voltage, this considers that mainly potassium concentration is higher in the glass sample, its specific conductivity is also higher, thereby at high temperature be difficult to apply high DC electric field (very easily discharge), so can not induce the second harmonic generating effect effectively.We know that the resistance of semiconductor material descends with temperature and raises, and can remedy the slack-off deficiency of bringing of alkalimetal ion rate travel under the low temperature effectively so improve constantly polarizing voltage in cooling.Evidence, by the thermoaeization method after improving we at glass sample (as 60GeS
2-20Ga
2S
3-obtain second-order nonlinear polarizability in 20KBr) up to 5.7pm/V, and can at room temperature steady in a long-termly exist.Glass of the present invention is frequency multiplication and the photoelectricity modulation material that has development potentiality.The development of optoelectronics industry and the raising of military project strength all had important effect.
Description of drawings
Fig. 1 is that sample current changes in embodiment 1 polarization process.
Fig. 2 is a sample visible-near-infrared spectrum test pattern before and after embodiment 1 polarization.
Fig. 3 is the XRD test pattern of sample before and after embodiment 1 polarization.
Fig. 4 is embodiment 1 a sample Maker striped test pattern.
Fig. 5 is that sample current changes in embodiment 2 and 3 polarization processes.
Fig. 6 is a sample visible-near-infrared spectrum test pattern before and after embodiment 2 polarization.
Fig. 7 is a sample visible-near-infrared spectrum test pattern before and after embodiment 3 polarization.
Embodiment
To main contents of the present invention be described by embodiment below, but not only be confined to these examples.
Embodiment 1
Formulating of recipe: adopt germanium, gallium, sulphur and Potassium Bromide quaternary system, design of components is as follows:
| GeS 2 | Ga 2S 3 | KBr |
| 60 | 20 | 20 |
The admixtion preparation:
Adopting highly purified elemental Germanium, gallium, sulphur (＞99.999%) and compound Potassium Bromide (＞99.9%) respectively is raw material, carries out formula calculation by the composition shown in the table 1.
The preparation of glass sample:
At first the quartz ampoule pipe that admixtion is housed is vacuumized, subsequently that sealing-in is good quartz ampoule pipe places and waves electric furnace, keeps during heating waving, with fusing and the clear quality of improving glass metal.Temperature of fusion is 950 ℃, and soaking time is 10 hours.The glass that fusing is good is together with quartz ampoule pipe quenching in air.Quartz ampoule pipe behind the quenching directly moved in the retort furnace anneal.Retort furnace is warming up to 280 ℃ in advance.Insulation after 2 hours is closed electric furnace in retort furnace, and glass specimen cools to room temperature with the furnace.At last glass sample is cut and optical polish.The gained sample is cylindrical transparent glass thin slice.
The processing of thermoaeization of glass sample:
At first sample is securely fixed between the upper/lower electrode together with the silica glass thin slice, put into subsequently and add electrothermal stove and heat, after reaching 180 ℃, temperature applies the 0.8kv high-voltage dc immediately, be incubated and open the electric furnace lid immediately after 20 minutes, furnace cooling 5 minutes takes out sample the polarizing voltage that raises simultaneously afterwards to 0.9kv, at room temperature cool off 20 minutes after, the polarizing voltage that raises is once more removed extra electric field at last to 1kv cooling 20 minutes.
The test of Maker striped:
Sample after the polarization is tested second harmonic intensity by the Maker the Schlieren method immediately.Adopt Pulse Nd: YAG laser apparatus (Spectra-Physics GCR-11) is as LASER Light Source, fundamental frequency lambda1-wavelength 1064nm, the parallel glass sample surface that is incident in.Outgoing frequency doubled light wavelength 532nm, photomultiplier (Hamamatsu Photonics R955) is used in the detection of frequency doubled light.Use digital oscilloscope (Hewlett-Packard54522A) to show the intensity of second harmonic simultaneously.
Test-results:
Resulting glass specimen is done following performance measurement:
(1) sample current changes test in the polarization process: test result such as Fig. 1.As seen from Figure 1, sample is applied different voltage, electric current all reached capacity after 20 minutes, and this is that in view of the above, we determine that the polarization time is 20 minutes because the concentration of contained potassium ion is certain in the sample.Among the figure, 1 is 0.787KV/mm, and 2 is 0.535KV/mm;
(2) before and after the polarization sample visible-the near infrared spectrum test
As seen from Figure 2, sample visible-near infrared spectrum before and after polarization changes very not obvious, so polarization process can not influence the good optical property of sample itself as can be known, as wide transparency range, high transmitance.Among Fig. 2, before the 3 representative polarization, after the 4 representative polarization.
(3) XRD of sample test before and after the polarization
As seen from Figure 3, XRD spectrum does not almost change before and after the polarization, and sample interior does not have crystallization after old friend's thermal treatment, and sample has shown good thermostability, and this further improvement to thermoae metallization processes is very useful.Among Fig. 3, after the 5 representative polarization, before the 6 representative polarization;
(4) sample Maker striped test
As seen from Figure 4, sample after the polarization has produced Maker speckle pattern interferometry figure clearly, can calculate relevant wavelength by 40 ° of the pairing angles of its peak value is 6 μ m, be slightly larger than the non-linear layer thickness 5.6 μ m of sample, this has just affirmed that second order nonlinear effect is mainly determined by the small thin layer near the positive column.
Embodiment 2～3
In each of the embodiments described below, the preparation method of glass is with embodiment 1, and the different glass composition that is adopted is listed in table 2.
The glass of table 2 embodiment 2～3 is formed (mol%)
| Embodiment | GeS 2 | Ga 2S 3 | KBr |
| 2 | 70 | 15 | 15 |
| 3 | 50 | 25 | 25 |
Embodiment 2～3 every The performance test results such as Fig. 5,6 and 7.
Among Fig. 5, on behalf of embodiment 2,8,7 represent embodiment 3.
Among Fig. 6 and Fig. 7, before the 9 representative polarization, after the 10 representative polarization.
Claims (5)
1. the thermoaeization method with sulfur-halogen glass of high second-order nonlinear polarizability is characterized in that, improves constantly polarizing voltage in sulfur-halogen glass sample process of cooling.
2. method according to claim 1 is characterized in that, comprises the steps:
The sulfur-halogen glass sample is placed between two stainless steel electrodes, between upper/lower electrode and sample surfaces, place the silica glass thin slice simultaneously, fixing;
Be heated to the high-voltage dc of 150～200 ℃ of after-applied 0.5～0.8kv, be incubated 10～30 minutes, stop heating, cooled off 1～10 minute, sample is taken out, and while boosted voltage to 0.6～0.9kv is after cooling off 10～30 minutes under 10～35 ℃ the environment, boosted voltage to 0.91～1.0kv cooled off 10～30 minutes once more, promptly obtained to have the sulfur-halogen glass of high second-order nonlinear polarizability.
3. method according to claim 2 is characterized in that, the silica glass sheet thickness is 0.05～0.2mm.
4. according to the sulfur-halogen glass with high second-order nonlinear polarizability of claim 1, the preparation of 2 or 3 described methods.
5. sulfur-halogen glass according to claim 4 is characterized in that glass consists of:
(70-x)GeS
2-(15+x/2)Ga
2S
3-(15+x/2)RH
Wherein: x=0～20, R=Na or K; H=Cl or Br.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610024737 CN1821132A (en) | 2006-03-16 | 2006-03-16 | Sulfer-halogen glass having high second-order non-linear polarizability and its heat polarizing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610024737 CN1821132A (en) | 2006-03-16 | 2006-03-16 | Sulfer-halogen glass having high second-order non-linear polarizability and its heat polarizing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1821132A true CN1821132A (en) | 2006-08-23 |
Family
ID=36922732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610024737 Pending CN1821132A (en) | 2006-03-16 | 2006-03-16 | Sulfer-halogen glass having high second-order non-linear polarizability and its heat polarizing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1821132A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108681181A (en) * | 2018-05-18 | 2018-10-19 | 上海大学 | The laser assisted thermal poling device and method of micro- second-order nonlinear polarizability optical element |
| CN108732846A (en) * | 2018-05-18 | 2018-11-02 | 上海大学 | Being prepared using grid electrode thermal poling has the preparation method of periodically micro- second-order nonlinear polarizability optical element |
| CN109270613A (en) * | 2018-09-05 | 2019-01-25 | 上海大学 | The preparation method of visible-echelette diffraction grating is prepared using the micro- thermal poling technique of grid electrode |
| CN111273393A (en) * | 2020-03-30 | 2020-06-12 | 浙江师范大学 | Four-core optical fiber thermal polarization structure with high second-order nonlinear polarizability |
| CN111273392A (en) * | 2020-03-30 | 2020-06-12 | 浙江师范大学 | Novel optical fiber thermal polarization structure based on thermal polarization electric field evolution |
| CN113165881A (en) * | 2018-10-18 | 2021-07-23 | 康宁股份有限公司 | Graphene doping by thermal polarization |
-
2006
- 2006-03-16 CN CN 200610024737 patent/CN1821132A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108681181A (en) * | 2018-05-18 | 2018-10-19 | 上海大学 | The laser assisted thermal poling device and method of micro- second-order nonlinear polarizability optical element |
| CN108732846A (en) * | 2018-05-18 | 2018-11-02 | 上海大学 | Being prepared using grid electrode thermal poling has the preparation method of periodically micro- second-order nonlinear polarizability optical element |
| CN108732846B (en) * | 2018-05-18 | 2020-09-04 | 上海大学 | Method for preparing optical element with periodic microscopic second-order nonlinear polarizability by adopting grid electrode hot polarization |
| CN109270613A (en) * | 2018-09-05 | 2019-01-25 | 上海大学 | The preparation method of visible-echelette diffraction grating is prepared using the micro- thermal poling technique of grid electrode |
| CN113165881A (en) * | 2018-10-18 | 2021-07-23 | 康宁股份有限公司 | Graphene doping by thermal polarization |
| CN113165881B (en) * | 2018-10-18 | 2024-04-05 | 康宁股份有限公司 | Graphene doping by thermal polarization |
| CN111273393A (en) * | 2020-03-30 | 2020-06-12 | 浙江师范大学 | Four-core optical fiber thermal polarization structure with high second-order nonlinear polarizability |
| CN111273392A (en) * | 2020-03-30 | 2020-06-12 | 浙江师范大学 | Novel optical fiber thermal polarization structure based on thermal polarization electric field evolution |
| CN111273393B (en) * | 2020-03-30 | 2024-01-26 | 浙江师范大学 | Four-core optical fiber thermal polarization structure with high second-order nonlinear polarization rate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kamitsos et al. | Raman and Infrared Structural Investigation of x Rb2O⊙(1− x) GeO2 Glasses | |
| Nasu et al. | Optical third-harmonic generation from some high-index glasses | |
| CN1821132A (en) | Sulfer-halogen glass having high second-order non-linear polarizability and its heat polarizing method | |
| JP5255611B2 (en) | GLASS SUBSTRATE FOR DISPLAY, PROCESS FOR PRODUCING THE SAME AND DISPLAY USING THE SAME | |
| Nasu et al. | Second-and third-order optical non-linearity of homogeneous glasses | |
| Kang et al. | Influences of Fe3+ ions on rapid growth and laser-induced nonlinear refraction of potassium dihydrogen phosphate crystal | |
| Ding et al. | Oriented surface crystallization of lithium niobate on glass and second harmonic generation | |
| Dussauze et al. | Polarization mechanisms and structural rearrangements in thermally poled sodium-alumino phosphate glasses | |
| Dussauze et al. | Correlation of large SHG responses with structural characterization in borophosphate niobium glasses | |
| Zhang et al. | Enhanced thermostability, thermo‐optics, and thermomechanical properties of barium gallo‐germanium oxyfluoride glasses and glass‐ceramics | |
| Narazaki et al. | Effect of poling temperature on optical second harmonic intensity of sodium zinc tellurite glasses | |
| Shen et al. | Preparation and third-order optical nonlinearity of glass ceramics based on GeS2–Ga2S3–CsCl pseudo-ternary system | |
| Tong et al. | Effect of sodium addition and thermal annealing on second-order optical nonlinearity in thermally poled amorphous Ta2O5 thin films | |
| Nasu et al. | Second harmonic generation from an electrically polarized TiO2-containing silicate glass | |
| Chen et al. | Optical nonlinear, EPR, second harmonic generation and Faraday rotation studies on diamagnetic solid: Influence of thermal poling | |
| Khaled et al. | Generation of second harmonics in Ge-doped SiO 2 thin films by ultraviolet irradiation under poling electric field | |
| Inoue et al. | Laser patterning of non-linear optical Bi2ZnB2O7 crystal lines in glass | |
| CN1884167A (en) | Selenium-base chalcohalide glass and method for preparing same | |
| RU2429210C1 (en) | Nanostructured polarised glass and method of its production | |
| Zhang et al. | Enhanced third-order optical nonlinearity and photon luminescence of Sn 2+ in gold nanoparticles embedded chalcogenide glasses | |
| Miedzinski et al. | Nonlinear optical properties of TeO2-P2 O5-ZnO-LiNbO3 glass doped with Er3+ ions | |
| JP2012229154A (en) | Glass substrate for display, method for producing the same, and display using the same | |
| Narazaki et al. | Effect of Poling Temperature on Optical Second‐Harmonic Intensity of Lithium Sodium Tellurite Glass | |
| Xi et al. | Second-order optical nonlinearity in bulk PbO/B2O3 glass | |
| Pernice et al. | Electric field induced structural modification and second order optical nonlinearity in potassium niobium silicate glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |