CN117447078A - Method for adjusting nonlinear refractive index of optical functional glass - Google Patents
Method for adjusting nonlinear refractive index of optical functional glass Download PDFInfo
- Publication number
- CN117447078A CN117447078A CN202311449821.9A CN202311449821A CN117447078A CN 117447078 A CN117447078 A CN 117447078A CN 202311449821 A CN202311449821 A CN 202311449821A CN 117447078 A CN117447078 A CN 117447078A
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- CN
- China
- Prior art keywords
- heavy metal
- solution
- acetate
- glass
- optical functional
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- 239000011521 glass Substances 0.000 title claims abstract description 39
- 230000003287 optical effect Effects 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 150000004703 alkoxides Chemical class 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 229940046892 lead acetate Drugs 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910002656 O–Si–O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910008341 Si-Zr Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229910006339 Si—Pb Inorganic materials 0.000 description 1
- 229910006682 Si—Zr Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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
- C03C4/00—Compositions for glass with special properties
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
Abstract
The invention discloses a method for adjusting nonlinear refractive index of optical functional glass, and relates to optical functional glass processing technology. Adding heavy metal solution into optical functional glass precursor liquid, stirring and reacting to prepare sol, and finally standing, ageing and drying to obtain the optical functional glass. The invention effectively regulates the nonlinear refractive index of the glass, brings new optical characteristics to the glass, and expands the application of the glass in the photoelectric field.
Description
Technical Field
The invention belongs to the technical field of optical functional glass, and particularly relates to a method for adjusting nonlinear refractive index of optical functional glass.
Background
The silica gel glass has excellent physical and chemical properties, excellent optical stability and high transparency, and can be used as an ideal substrate for solid phase immobilization of optical functional materials.
At present, the research on the nonlinear refractive index regulation of the optical functional glass is not perfect, so how to effectively regulate the nonlinear refractive index of the optical functional glass is also a hot spot direction of the current research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for adjusting the nonlinear refractive index of optical functional glass, which is realized by the following steps:
a method of adjusting the nonlinear refractive index of a optically functional glass comprising the steps of:
(1) Preparing a precursor liquid: dissolving tetraethyl orthosilicate in an ethanol water solution, adding N, N-dimethylformamide, and uniformly mixing and stirring to obtain a precursor solution;
(2) Preparing heavy metal alkoxide solution:
dissolving heavy metal acetate in a mixed solution of ethylene glycol methyl ether and acetic acid to prepare a heavy metal alkoxide solution;
(3) Mixing the precursor solution and the heavy metal alkoxide solution according to the molar ratio of heavy metal to tetraethyl orthosilicate of 3:1, then dropwise adding nitric acid, and stirring for reaction to obtain sol, wherein the molar ratio of heavy metal to tetraethyl orthosilicate is 3:1;
(4) And placing the sol into a mold for standing and ageing, and drying to obtain the optical function glass.
Preferably, the mass concentration of the N, N-dimethylformamide in the precursor solution is 99.5%. The volume ratio of ethanol to water in the ethanol water solution is 2.57:1.
Further preferably, the mass concentration of the tetraethyl orthosilicate in the precursor solution is 93.2% -93.6%.
Preferably, the heavy metal acetate is at least one of lead acetate, zirconium acetate and cadmium acetate.
Preferably, the volume ratio of the propylene glycol to the acetic acid in the mixed solution in the step (2) is 2.37:1.
Further preferably, the mass concentration of heavy metal acetate in the heavy metal alkoxide solution is 6%.
Preferably, the nitric acid concentration is 68%.
Preferably, the time of standing and ageing in the step (4) is not less than 8 hours to several days.
Preferably, the drying temperature in the step (4) is 23 ℃, and the drying time is 60-120 days.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for adjusting nonlinear refractive index of optical functional glass, which is characterized in that heavy metal ions are added in the glass preparation process, so that the nonlinear refractive index of the glass is effectively adjusted, a few new optical characteristics are brought to the glass, and the application of the glass in the photoelectric field is expanded.
Drawings
FIG. 1 is an x-ray diffraction pattern of the optically functional glass prepared in examples 1-4;
FIG. 2 is an infrared spectrum of the optically functional glass prepared in examples 1-4;
FIG. 3 is a closed cell Z-scan curve of the optically functional glass prepared in examples 1-4 at picosecond pulsed laser energy.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
Weighing 12.5g TEOS, 17.6mL ethanol, 5.4mL water and 8.316g N, N-dimethylformamide, and mixing uniformly to obtain solution 1 # ；
Mixing ethylene glycol methyl ether and glacial acetic acid according to the volume ratio of 2.37:1 to obtain a mixed solution; 8.37g of lead acetate was weighed and dissolved in 33.7mL of the above mixed solution to obtain solution 2 # 。
Solution 1 to be formulated # And solution 2 # Slowly mixing, dropwise adding 1mL of nitric acid with the mass concentration of 68% to promote hydrolysis and polycondensation reaction, and continuously stirring at room temperature for 8 hours to obtain clear sol;
placing the sol into a plastic culture dish, sealing, standing, aging and drying for 8 hours to obtain the optical function glass, and marking the optical function glass as Si-Pb.
Example 2
Weighing 12.5g TEOS, 17.6mL ethanol, 5.4mL water and 8.316g N, N-dimethylformamide, and mixing uniformly to obtain solution 1 # ；
Mixing ethylene glycol methyl ether and glacial acetic acid according to the volume ratio of 2.37:1 to obtain a mixed solution; 8.41g of zirconium acetate was weighed and dissolved in 33.7mL of the above mixed solution to obtain solution 2 # 。
Solution 1 to be formulated # And solution 2 # Slowly mixing, dropwise adding 1mL of nitric acid with the mass concentration of 68% to promote hydrolysis and polycondensation reaction, and continuously stirring at room temperature for 8 hours to obtain clear sol;
placing the sol into a plastic culture dish, sealing, standing, aging and drying for 2 weeks to obtain the optical functional glass, and marking the optical functional glass as Si-Zr.
Example 3
Weighing 12.5g TEOS, 17.6mL ethanol, 5.4mL water and 8.316g N, N-dimethylformamide, and mixing uniformly to obtain solution 1 # ；
Mixing ethylene glycol methyl ether and glacial acetic acid according to the volume ratio of 2.37:1 to obtain a mixed solution; 6.85g of cadmium acetate is weighed and dissolved in 33.7mL of the mixed solution to obtain solution 2 # 。
Solution 1 to be formulated # And solution 2 # Slowly mixing, dropwise adding 1mL of nitric acid with the mass concentration of 68% to promote hydrolysis and polycondensation reaction, and continuously stirring at room temperature for 8 hours to obtain clear sol;
and placing the sol into a plastic culture dish, sealing, standing, aging and drying for 2 weeks to obtain the optical functional glass, and marking the optical functional glass as Si-Cd.
Example 4
Weighing 12.5g TEOS, 17.6mL ethanol, 5.4mL water and 8.316g N, N-dimethylformamide, and mixing uniformly to obtain solution 1 # ；
Mixing ethylene glycol methyl ether and glacial acetic acid according to the volume ratio of 2.37:1 to obtain a mixed solution; 8.16g of cerium acetate was weighed and dissolved in 33.7mL of the above mixed solution to obtain solution 2 # 。
Solution 1 to be formulated # And solution 2 # After slow mixing1mL of nitric acid with the mass concentration of 68% is dropwise added to promote hydrolysis and polycondensation reaction, and clear sol is obtained after continuous stirring for 8 hours at room temperature;
placing the sol into a plastic culture dish, sealing, standing, aging and drying for 2 weeks to obtain the optical functional glass, and marking the optical functional glass as Si-Ce.
Characterization of the properties:
as can be seen from FIG. 1, only one of the four XRD patterns of the optically functional glass described in examples 1-4 has a wider SiO centered at 2θ=25° 2 Diffraction peaks, no sharp diffraction peaks.
As can be seen from FIG. 2, the spectrum of the optically functional glass of the present invention corresponds to 3446cm -1 And 1658cm -1 Is the absorption peak band of the adsorbed water; located at 460cm -1 And 440cm -1 Nearby is Si-O-Si bending vibration characteristic peak, 795cm -1 The vicinity is O-Si-O symmetrical telescopic vibration characteristic peak, 1066cm -1 Nearby is asymmetric Si-O-Si antisymmetric stretching vibration characteristic peak 1565cm -1 、1535cm -1 And 1385cm -1 Nearby is a c=o vibration characteristic peak; whereas 900cm -1 And 948cm -1 The nearby Si-OH bending vibration characteristic peaks are generated due to insufficient hydrolysis. 660cm -1 And 560cm -1 The nearby vibration characteristic peaks are caused by electronic structural defects.
As can be seen from fig. 3, the same incident energy increases the nonlinear refractive index with increasing radius of the heavy metal ions. Meanwhile, heavy metal ions have large mass and ion radius and high polarizability, and are formed on SiO 2 Heavy metal ions are added into the glass matrix to form groups with very high polarizability, and electron clouds are easy to deform. The metal oxide glass has high refractive index, excellent infrared light transmission performance and high third-order nonlinear optical polarization rate, so that the nonlinear optical response of the composite gel glass is enhanced. The more nonlinear optical properties thereof are as the ion radius increases.
It should be noted that the above-mentioned embodiments are only a few specific embodiments of the present invention, and it is obvious that the present invention is not limited to the above embodiments, but other modifications are possible. All modifications directly or indirectly derived from the disclosure of the present invention will be considered to be within the scope of the present invention.
Claims (9)
1. A method for adjusting the nonlinear refractive index of optically functional glass, comprising the steps of:
(1) Preparing a precursor liquid: dissolving tetraethyl orthosilicate in an ethanol water solution, adding N, N-dimethylformamide, and uniformly mixing and stirring to obtain a precursor solution;
(2) Preparing heavy metal alkoxide solution:
dissolving heavy metal acetate in a mixed solution of ethylene glycol methyl ether and acetic acid to prepare a heavy metal alkoxide solution;
(3) Mixing the precursor solution and the heavy metal alkoxide solution according to the molar ratio of heavy metal to tetraethyl orthosilicate of 3:1, then dropwise adding nitric acid, and stirring for reaction to obtain sol, wherein the molar ratio of heavy metal to tetraethyl orthosilicate is 3:1;
(4) And placing the sol into a mold for standing, aging and drying to obtain the optical functional glass.
2. The method according to claim 1, wherein the mass concentration of N, N-dimethylformamide in the precursor solution is 99.5%.
3. The method according to claim 1, wherein the mass ratio of ethanol to water in the aqueous ethanol solution is 2.57:1.
4. The method according to claim 1, wherein the mass concentration of tetraethyl orthosilicate in the precursor solution is 93.2% -93.6%.
5. The method of claim 1, wherein the heavy metal acetate is at least one of lead acetate, zirconium acetate, cadmium acetate, cerium acetate.
6. The method of claim 1, wherein the mixed solution of step (2) has a volume ratio of propylene glycol to acetic acid of 2.37:1.
7. The method according to claim 1, wherein the heavy metal alkoxide solution in step (2) has a heavy metal acetate mass concentration of 6%.
8. The method according to claim 1, wherein the mass concentration of nitric acid is 68%.
9. The method of claim 1, wherein the time for the standing and aging in step (4) is not less than 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311449821.9A CN117447078A (en) | 2023-11-02 | 2023-11-02 | Method for adjusting nonlinear refractive index of optical functional glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311449821.9A CN117447078A (en) | 2023-11-02 | 2023-11-02 | Method for adjusting nonlinear refractive index of optical functional glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117447078A true CN117447078A (en) | 2024-01-26 |
Family
ID=89592591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311449821.9A Pending CN117447078A (en) | 2023-11-02 | 2023-11-02 | Method for adjusting nonlinear refractive index of optical functional glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117447078A (en) |
-
2023
- 2023-11-02 CN CN202311449821.9A patent/CN117447078A/en active Pending
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