CN109320093B - Transparent glass-ceramic material and preparation method thereof - Google Patents
Transparent glass-ceramic material and preparation method thereof Download PDFInfo
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- CN109320093B CN109320093B CN201811364792.5A CN201811364792A CN109320093B CN 109320093 B CN109320093 B CN 109320093B CN 201811364792 A CN201811364792 A CN 201811364792A CN 109320093 B CN109320093 B CN 109320093B
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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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/16—Halogen containing crystalline phase
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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Abstract
The invention discloses a transparent microcrystalline glass material, the composition formula of which is 20GeS2•35Ga2S345CsCl obtained by microcrystallization heat treatment of a Cl-doped Ge-Ga-S chalcogenide glass material, and Cl is doped into the Ge-Ga-S chalcogenide glass material in the form of a CsCl compound. The transparent glass-ceramic material disclosed by the invention has the transmittance of 80-85%, and the third-order nonlinear refractive index can reach 1.47 multiplied by 10‑18 m2And/w. The transparent glass-ceramic material has high permeability, good chemical stability and thermal stability, fast optical response, easy fiber forming and film forming, easy mechanical processing and the like, is an excellent non-resonant nonlinear optical material for preparing an ultrafast All-optical switch (All optical switch AOS) device, and can play a good practical value in the future optical field.
Description
Technical Field
The invention relates to a transparent glass ceramic, in particular to a transparent glass ceramic material and a preparation method thereof.
Background
With the rapid development of current information technology, the core position of the photoelectric technology is more and more shown, and the development of a novel nonlinear optical material is an important component of the development of the photoelectric technology. Glass is transparent and optically isotropic in most wavelengths and therefore generally exhibits only third-order nonlinearity, and glass has high thermal and chemical stability, and more importantly, glass is easy to prepare and process, so that it is very attractive as a nonlinear optical material. In a plurality of glass systems, the outermost layer electron cloud of chalcogenide glass chalcogen elements (S, Se and Te) is easy to distort under the induction of a strong optical field, so that the third-order nonlinear performance of the chalcogenide glass is superior to that of common oxide glass, and the chalcogenide glass has the nonlinear response time from femtosecond to sub-femtosecond.
In the prior literature reports, the hardness, the rare earth luminous intensity, the nonlinear optical performance and the like of glass can be enhanced by precipitating crystal particles with the size of micron or less in a chalcogenide glass network by heat treatment. The improvement of the third-order nonlinearity of chalcogenide glass by using the size effect generated by the nano-crystal or metal particle is a key point in the related fields in the future, but the current research is not focused enough, and many problems need to be solved, such as the selection of a nucleating agent, the acquisition of a reasonable precipitated crystal phase, the improvement of the transmittance and the third-order nonlinearity, and the like. In view of this, the invention provides a transparent glass-ceramic material and a preparation method thereof.
Disclosure of Invention
The invention aims to solve the technical problem of providing a transparent glass ceramic material with high transmittance and good third-order nonlinear performance and a preparation method thereof aiming at the defects of the existing inorganic heat-insulating material.
The technical scheme adopted by the invention for solving the technical problems is as follows: a transparent microcrystalline glass material has a composition formula of 20GeS2·35Ga2S345CsCl obtained by microcrystallization heat treatment of a Cl-doped Ge-Ga-S chalcogenide glass material, and Cl is doped into the Ge-Ga-S chalcogenide glass material in the form of a CsCl compound.
A preparation method of a transparent glass ceramic material comprises the following steps:
(1) burdening and vacuumizing: preparing raw materials of elemental germanium, elemental gallium, elemental sulfur and cesium chloride according to a ratio, uniformly mixing, putting the mixed raw materials into a quartz tube, and vacuumizing to 10 DEG-4～10-7Pa, packaging the raw materials in a closed quartz tube;
(2) high-temperature melting and quenching: putting the quartz tube packaged with the raw materials into a heating furnace for high-temperature melting, wherein the heating temperature is 300-900 ℃, the heating time is 18-36 hours, obtaining a melt in the quartz tube after heating, then immersing the quartz tube into distilled water at-5-45 ℃ to quench the packaged melt, taking out immediately after wall removal, and obtaining a CsCl-doped Ge-Ga-S chalcogenide glass material semi-finished product in the quartz tube;
(3) annealing and cooling: annealing the CsCl-doped Ge-Ga-S chalcogenide glass material semi-finished product together with the quartz tube, wherein the annealing temperature is 300-350 ℃, the annealing time is 8-15 h, cooling the quartz tube and the chalcogenide glass material in the quartz tube to room temperature at the cooling rate of 1-20 ℃/h after the annealing is finished, and opening the quartz tube to obtain the CsCl-doped Ge-Ga-S chalcogenide glass material finished product;
(4) microcrystal the CsCl-doped Ge-Ga-S chalcogenide glass material finished product at the temperature of 320-380 DEG CCarrying out heat treatment for 3-10 h to obtain the transparent glass ceramic material with the composition formula of 20GeS2·35Ga2S3·45CsCl。
Preferably, the microcrystallization heat treatment time in the step (4) is 5 hours. The third-order nonlinearity of the transparent glass-ceramic material obtained by 5h of microcrystallization heat treatment is 4 times higher than that of matrix glass and 230 times higher than that of silicon dioxide glass, and the transparent glass-ceramic material has better third-order nonlinearity.
Preferably, the raw materials of the elemental germanium, the elemental gallium and the elemental sulfur used in the step (1) have the purity of more than 99.999 percent.
Compared with the prior art, the invention has the advantages that: the transparent microcrystalline glass material disclosed by the invention is obtained by carrying out microcrystallization heat treatment on a Ge-Ga-S chalcogenide glass material doped with Cl. The transparent microcrystalline glass material has a transmittance of 80-85%, and a third-order nonlinear refractive index of 1.47 × 10-18m2And/w. The transparent glass-ceramic material has high permeability, good chemical stability and thermal stability, fast optical response, easy fiber forming and film forming, easy mechanical processing and the like, is an excellent non-resonant nonlinear optical material for preparing an ultrafast All-optical switch (All optical switch AOS) device, and can play a good practical value in the future optical field.
Drawings
FIG. 1 is a schematic structural diagram of a Z-scan experimental apparatus;
FIG. 2 is a Z-scan test result graph of glass material samples of examples 1 to 4 and comparative example;
FIG. 3 is a graph showing the transmission and absorption spectra in the visible wavelength range (400 to 850nm) of the glass material samples of examples 1 to 4 and comparative example;
fig. 4 shows the optical band gaps of the glass material samples of examples 1 to 4 and comparative example.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
The composition formula of the transparent microcrystalline glass material of example 1 was 20GeS2·35Ga2S345CsCl prepared from Cl-doped Ge-Ga-The chalcogenide glass material is obtained by micro-crystallization heat treatment, and Cl is doped into the Ge-Ga-S chalcogenide glass material in the form of CsCl compound. The preparation method of the transparent glass-ceramic material comprises the following steps:
(1) burdening and vacuumizing: preparing raw materials of elemental germanium, elemental gallium, elemental sulfur and cesium chloride according to a ratio, uniformly mixing, putting the mixed raw materials into a quartz tube, and vacuumizing to 10 DEG-7Pa, packaging the raw materials in a closed quartz tube;
(2) high-temperature melting and quenching: putting the quartz tube packaged with the raw materials into a heating furnace for high-temperature melting, wherein the heating temperature is 900 ℃, the heating time is 24 hours, obtaining a melt in the quartz tube after the heating is finished, then immersing the quartz tube into distilled water at the temperature of 25 ℃ to quench the packaged melt, taking out the quartz tube immediately after the quartz tube is detached from the wall, and obtaining a CsCl-doped Ge-Ga-S chalcogenide glass material semi-finished product in the quartz tube;
(3) annealing and cooling: annealing the semi-finished product of the CsCl-doped Ge-Ga-S chalcogenide glass material together with the quartz tube, wherein the annealing temperature is 350 ℃, the annealing time is 10 hours, cooling the quartz tube and the chalcogenide glass material in the quartz tube to the room temperature at the cooling rate of 3 ℃/h after the annealing is finished, and opening the quartz tube to obtain the CsCl-doped Ge-Ga-S chalcogenide glass material finished product;
(4) carrying out microcrystallization heat treatment on the CsCl-doped Ge-Ga-S chalcogenide glass material finished product at the temperature of 350 ℃ for 3h to obtain the transparent glass ceramic material with the composition formula of 20GeS2·35Ga2S3·45CsCl。
The transparent glass-ceramic materials of examples 2 to 4 are different from example 1 in that the microcrystallization heat treatment time in step (4) of examples 2 to 4 is 5 hours, 7 hours, and 10 hours, respectively.
For comparison, a matrix glass was selected as a comparative example. The comparative example is different from example 1 in that the glass material of the comparative example is prepared without the microcrystallization heat treatment process of step (4).
The glass materials of examples 1 to 4 and comparative example were transparent in appearance.
For the glass material samples of examples 1 to 4 and comparative example, the third-order nonlinear optical parameters at a wavelength of 800nm were respectively detected by a Z-scan experiment. The experimental setup is shown in figure 1. The used pumping light source is a titanium gem tunable femtosecond laser from the United states Coherent company, the output pulse is 200fs, the wavelength adjusting range is 700-1010 nm, and the power stability is +/-3%. After the pumping light passes through a broadband total reflection mirror, a broadband semi-transmission semi-reflection spectroscope (the reflectivity and the transmissivity are 45% and 55% respectively) is divided into two beams of light, one beam of light is used as a reference light source of incident power and is detected by a detector 1, the other beam of light is focused by a biconvex mirror and irradiates a glass sample, and the transmitted beam of light is received by a detector 2. The detector 1 and the detector 2 are respectively input into a Coherent company EM2000 type double-channel power meter. During the experiment, the position of the sample is adjusted through the stepping motor controller, and the reading of the power meter is recorded, so that a group of Z scanning data with one-to-one correspondence of the Z position and the transmittance is obtained. The above tests were carried out at room temperature.
The Z-scan test results of the glass material samples of examples 1-4 and comparative example are shown in FIG. 2. As can be seen from fig. 2, the peak-to-valley differences in the Z-scan curves of the samples of examples 1 to 4 subjected to the microcrystallization heat treatment exhibited a tendency to increase first and then decrease compared to the matrix glass.
Measured and calculated, the nonlinear refractive index n of the matrix glass sample under 800nm2Is 0.486X 10-18m2/w, nonlinear refractive index n at 800nm for the transparent glass-ceramic materials of examples 1 to 42Are respectively 1.41 multiplied by 10-18m2/w、1.47×10-18m2/w、1.44×10-18m2/w、0.248×10-18m2And/w. Physical, optical and TONL parameters of the glass material samples of examples 1 to 4 and comparative examples are shown in table 1.
As is apparent from Table 1, the glass materials of examples 1 to 3 have the nonlinear refractive index n2All exceeding the matrix glass. Glass materials of comparative examples 1 to 4, which have a non-linear refractive index n2Shows a tendency of increasing first and then decreasing in absolute value of (a), wherein the non-linearity of example 2 of the microcrystallization heat treatment for 5 hoursRefractive index n2Non-linear refractive index n of maximum, microcrystallized, heat treated 10h sample2Drops significantly below the matrix glass and changes the sign of its nonlinearity. The main reason for this phenomenon is that the chemical bond inside the glass changes as the microcrystallization heat treatment time increases. According to band theory, Eg is a key factor in determining the dispersion (i.e., wavelength dependence) of the TONL characteristics of semiconductor and node materials. Since the hv/Eg of the host glass at 800nm is below the TPA edge, the defect absorption at the tail of the sample causes the laser-induced electron transition to trigger the secondary stark effect, causing the host glass to exhibit negative nonlinearity. After the microcrystallization heat treatment, Ga is contained2S3The presence of crystals, whose size is on the nanometer level, triggers strong local electrons by the laser radiation, so that the nonlinearity becomes positive again. With Ga2S3The increase in crystal size and volume fraction limits the dielectric effect of electrons, which in turn translates into negative nonlinearity.
TABLE 1 physical, optical and TONL parameters of samples of glass materials of examples 1-4 and comparative examples
FIG. 3 shows the transmission and absorption spectra in the visible wavelength range (400 to 850nm) of the glass material samples of examples 1 to 4 and comparative example. As can be seen from fig. 3, the transmittance of the samples of examples 1 to 4 subjected to the microcrystallization heat treatment tended to increase and then decrease, and particularly, the transmittance of the samples subjected to the heat treatment for 10 hours was significantly decreased in the visible light band. The reason for this is that as the temperature of the microcrystallization heat treatment increases, the crystal growth time becomes too long, and the size of the precipitated crystal grains increases, so that the scattering loss increases, and the transmittance of the sample decreases, or even the sample loses transparency. When the grain size is smaller than the wavelength of visible light, the scattering intensity mainly depends on the ratio of the grain radius to the wavelength of incident light and is related to the ratio of the refractive indexes of the scatterer and the surrounding medium according to the Rayleigh scattering model. Therefore, the scattering loss is proportional to the grain size to the power of 6 at a constant ratio of the refractive index of the scatterer to the refractive index of the surrounding medium, and the scattering loss increases with decreasing wavelength at a constant grain size.
Fig. 3 also shows transmission and absorption spectra of the glass material samples of examples 1 to 4 and comparative example. It can be seen that the short-wave absorption edges of the glass samples of examples 1 to 4 are clearly located at about 400 um. The cut-off edge with long wavelength corresponding to the multiphoton process is about 2500 um. With the increase of the microcrystallization heat treatment temperature, the transmittance of the IR characteristic is sufficiently maintained by the sample, the average transmittance is between 80% and 85%, the decrease of the transmittance is probably caused by the non-uniformity of the glass, and the error can be reduced and is basically ignored in terms of the overall transmittance performance of the glass. In the transmission spectrum, the absorption band is visible and is suitable for about 1932um, corresponding to H2Impurity absorption of O (as observed in the spectrum in particular). On the one hand, water on the surface of the introduced raw materials leads to the formation of impurities during the glass production process; on the other hand, atmospheric water and oxygen are unavoidable, which will cause partial devitrification of the glass, but since the glass has been subjected to polishing treatment, this part of the influencing factors will not cause the test problem.
The optical band gaps of the glass material samples of examples 1 to 4 and comparative example are shown in fig. 4.
In FIGS. 2 to 4, GGC-0, GGC-3, GGC-5, GGC-7 and GGC-10 represent comparative examples, example 1,
glass samples of example 2, example 3, and example 4.
Claims (3)
1. The transparent microcrystalline glass material is characterized in that the composition formula of the transparent microcrystalline glass material is 20GeS2•35Ga2S345CsCl obtained by microcrystallizing a Ge-Ga-S chalcogenide glass material doped with Cl and doping Cl in the Ge-Ga-S chalcogenide glass material in the form of a CsCl compound, the method for producing the transparent microcrystalline glass material comprising the steps of:
(1) burdening and vacuumizing: preparing the raw materials according to the proportionUniformly mixing elemental germanium, elemental gallium, elemental sulfur and cesium chloride, putting the mixed raw materials into a quartz tube, and vacuumizing to 10 DEG-4～10-7Pa, packaging the raw materials in a closed quartz tube;
(2) high-temperature melting and quenching: putting the quartz tube packaged with the raw materials into a heating furnace for high-temperature melting, wherein the heating temperature is 300-900 ℃, the heating time is 18-36 hours, obtaining a melt in the quartz tube after heating, then immersing the quartz tube into distilled water at-5-45 ℃ to quench the packaged melt, taking out immediately after wall removal, and obtaining a CsCl-doped Ge-Ga-S chalcogenide glass material semi-finished product in the quartz tube;
(3) annealing and cooling: annealing the CsCl-doped Ge-Ga-S chalcogenide glass material semi-finished product together with the quartz tube, wherein the annealing temperature is 300-350 ℃, the annealing time is 8-15 h, cooling the quartz tube and the chalcogenide glass material in the quartz tube to room temperature at the cooling rate of 1-20 ℃/h after the annealing is finished, and opening the quartz tube to obtain the CsCl-doped Ge-Ga-S chalcogenide glass material finished product;
(4) carrying out microcrystallization heat treatment on the CsCl-doped Ge-Ga-S chalcogenide glass material finished product at the temperature of 320-380 ℃ for 3-10 h to obtain a transparent glass ceramic material, wherein the composition formula is 20GeS2•35Ga2S3•45CsCl。
2. The transparent microcrystalline glass material according to claim 1, wherein the microcrystallization heat treatment time in step (4) is 5 h.
3. The transparent glass-ceramic material according to claim 1, wherein the raw materials of elemental germanium, elemental gallium and elemental sulfur used in step (1) have a purity of 99.999% or more.
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| CN110002747B (en) * | 2019-04-16 | 2021-07-27 | 宁波大学 | High-purity chalcohalide glass not easy to deliquesce and purification preparation method thereof |
| CN110862232A (en) * | 2019-11-12 | 2020-03-06 | 宁波大学 | Sulfur-based microcrystalline glass material and preparation method thereof |
| CN111393032B (en) * | 2020-04-13 | 2022-07-08 | Oppo广东移动通信有限公司 | Microcrystalline glass cover plate, flexible screen assembly, electronic equipment and microcrystalline glass cover plate processing method |
| RU2770494C1 (en) * | 2021-11-22 | 2022-04-18 | Федеральное государственное бюджетное учреждение науки Институт химии высокочистых веществ имени Г.Г. Девятых Российской академии наук | Method for producing extra-pure chalcogenide glasses containing gallium |
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