CN115432922B - Photo-thermal refraction glass and preparation method thereof - Google Patents
Photo-thermal refraction glass and preparation method thereof Download PDFInfo
- Publication number
- CN115432922B CN115432922B CN202211062625.1A CN202211062625A CN115432922B CN 115432922 B CN115432922 B CN 115432922B CN 202211062625 A CN202211062625 A CN 202211062625A CN 115432922 B CN115432922 B CN 115432922B
- Authority
- CN
- China
- Prior art keywords
- glass
- sio
- crystallization
- photo
- refractive index
- 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.)
- Active
Links
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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides photo-thermal refraction glass and a preparation method thereof, which mainly relate to the technical field of diffraction optics, and the photo-thermal refraction glass comprises the following components in percentage by weight: siO (SiO) 2 ：60.0～70.0％；ZnO：4.0～8.0％；Al 2 O 3 ：4.0～9.0％；Br：0.5～2％；F：2.0～4.0％；Ag 2 O：0.010～0.060％；CeO 2 ：0.010～0.050％；SnO 2 ：0.00～0.10％；Sb 2 O 3 ：0.00～0.40％；Na 2 O+K 2 O:16.0 to 25.0 percent; wherein Br/SiO 2 ：11～24×10 ‑3 。
Description
Technical Field
The invention mainly relates to the technical field of diffraction optics, in particular to photo-thermal refraction glass and a preparation method thereof.
Background
Laser technology is considered to be one of the indispensable tools for human intelligent society to survive and develop. Among the various types of high-energy solid state, fiber and gas lasers, high-performance semiconductor laser pumping sources are a critical core. However, semiconductor lasers as pumping sources have the following problems in terms of spectral quality: along with the working of the semiconductor laser, the device generates heat to raise the temperature, the wavelength of the semiconductor laser is sensitive to the temperature, wavelength drift can be caused, the spectrum linewidth is widened, mismatch between the center wavelength of the semiconductor laser and the absorption wavelength of the pumped gain medium is easily caused, and the output efficiency and the reliability of the semiconductor laser pumping in the high-power laser are affected. Therefore, wavelength locking and narrow linewidth of semiconductor lasers are critical.
The volume Bragg grating has the characteristics of spectrum selection and angle selection, light emitted by each unit of the laser array outer cavity can be selectively fed back to the adjacent unit, phase locking of the laser array outer cavity is achieved, the spectrum width is narrowed to one tenth, the far-field divergence angle is less than 1.5mrad, and the output quality and stability of laser beams are effectively improved. Bulk bragg gratings are critical in semiconductor lasers. As a base material for bulk Bragg gratings, high quality Photo-thermal refractive (PTR) glass is a prerequisite for obtaining high quality bulk Bragg gratings.
The development of PTR glass was originally traced back to the 40 s of the twentieth century, and the american scientist stokey found that glass was sensitized by the addition of a metal nucleating agent and a sensitizer, after irradiation with ultraviolet radiation or even higher wavelengths. The photo-opacifying glass, photosensitive coloring glass and full-color photosensitive glass are prepared. Lays a foundation for preparing photosensitive glass for volume holographic recording later. At the end of the 80 s of the twentieth century, glebov et Al based on a photosensitive glass proposed by Stookey, first melted a photosensitive glass using a Li-Si-Al system, the crystallites precipitated by this type of photosensitive glass being mainly [ Li ] 2 O·SiO 2 ]However, the volume Bragg grating prepared from the PTR glass has lower diffraction efficiency and does not have the requirement of laser beam spatial filtering. By the 90 s of the twentieth century, glebov et al developed PTR glass that could produce bragg gratings with high diffraction efficiency by optimizing the formulation. In the beginning of twenty-first century, the Glebov team first used PTR glass to prepare high-efficiency volume Bragg gratings with diffraction efficiency up to 95++. PTR glass is concerned with hot, a large amount of work is conducted to deeply explore the microscopic mechanism surrounding the photosensitive-nucleation-crystallization process of PTR glass, but few reports are made on index properties which are very concerned with the practical application of optical transmittance, refractive index modulation degree, temperature rise and the like of PTR glass products. In 2000-2003, corning Inc. of AmericaIn patent US6632759 and US7288495, ge-containing PTR glass materials are reported, whose refractive index modulation Δn at 633nm reaches 2.8x10 -4 No report on the updating of key indexes of more products is found later.
There is less concern about optical transmittance, optical loss of PTR glass, but this property is critical for its Bragg grating device application. The glass has high optical loss, photons are consumed in the working process, a large amount of heat is generated, the temperature of the device is increased, and the efficiency and the reliability of a laser system and equipment are damaged. Reducing optical loss in the visible band and longer band of PTR glass is a key problem to be solved in manufacturing Bragg gratings with high diffraction efficiency, and is also a primary premise for high-power laser application.
A significant portion of the optical loss in PTR glass results from the intrinsic absorption band generated during heat treatment (absorption band conditions are evaluated herein at 440nm glass transmittance), which is primarily affected by the glass formulation and treatment process. The chemical composition and the content of nucleation cluster substances in the glass are regulated and controlled by controlling the components of the glass formula, so that the partial absorption band can be modified.
PTR-based vitreous Bragg grating devices are used as bulk diffraction elements, and periodic modulation of the internal refractive index is a key factor in achieving efficient Bragg diffraction. Achieving periodic modulation of the refractive index requires that the PTR glass have a strong refractive index modulation capability, which is fundamentally due to the refractive index difference between sodium fluoride nanocrystals (n-1.32) and glass (n-1.49) that are precipitated during the crystallization process in the glass exposure region. To improve this property, it is necessary to try to precipitate more sodium fluoride crystallites in the exposed areas, while the unexposed areas are kept in a non-devitrified state. In order to continuously approach the ideal state, the photo-thermal transformation capability of PTR glass is improved, and the design regulation of the chemical formula of the glass is the most fundamental and important research aspect.
Disclosure of Invention
The invention aims to provide photo-thermal refraction glass and a preparation method thereof, which solve the technical problem of how to improve the refractive index modulation capability of PTR glass in the prior art.
The invention discloses photo-thermal refraction glass and a preparation method thereof, wherein the photo-thermal refraction glass comprises the following components in percentage by weight: siO (SiO) 2 ：60.0～70.0％；ZnO：4.0～8.0％；Al 2 O 3 ：4.0～9.0％；Br：0.5～2％；F：2.0～4.0％；Ag 2 O：0.010～0.060％；CeO 2 ：0.010～0.050％；SnO 2 ：0.00～0.10％；Sb 2 O 3 ：0.00～0.40％；Na 2 O+K 2 O:16.0 to 25.0 percent; wherein Br/SiO 2 ：11～24×10 -3 。
Further, the components of the composition are expressed in weight percent: siO (SiO) 2 ：60.0～70.0％；ZnO：4.0～8.0％；Al 2 O 3 ：4.0～9.0％；Br：0.5～2％；F：2.0～4.0％；Ag 2 O：0.010～0.060％；CeO 2 ：0.010～0.050％；SnO 2 ：0.00～0.10％；Sb 2 O 3 ：0.00～0.40％；Na 2 O+K 2 O:16.0 to 25.0 percent; wherein Br/SiO 2 ：11～24×10 -3 。
Further, the components of the composition in percentage by weight comprise: siO (SiO) 2 ：61.0～68.0％；ZnO：4.5～7.5％；Al 2 O 3 ：4.5～8.0％；Br：0.7～1.6％；F：2.3～3.1％；Ag 2 O：0.020～0.040％；CeO 2 ：0.022～0.036％；SnO 2 ：0.00～0.08％；Sb 2 O 3 ：0.00～0.35％；Na 2 O+K 2 O：16.5～23.5％；Br/SiO 2 ：11～20×10 -3 . Further, the components of the composition in percentage by weight comprise: siO (SiO) 2 ：61.0～67.6％；ZnO：5.8～6.9％；Al 2 O 3 ：4.6～6.8％；Br：0.7～1.3％；F：2.4～3.1％；Ag 2 O：0.024～0.040％；SnO 2 ：0～0.05％；Sb 2 O 3 ：0.1～0.32％；Na 2 O+K 2 O：16.6～23.2％；Br/SiO 2 ：11～15×10 -3 。
Further, the components of the composition in percentage by weight comprise: snO (SnO) 2 /SiO 2 ：0～11×10 -4 Preferably in the range of 4 to 6.5; and/or Sb 2 O 3 /SiO 2 ：0～46×10 -4 Preferably 19 to 46, more preferably 21 to 46.
Further, the components of the composition in percentage by weight comprise: (Na) 2 O+K 2 O)/Al 2 O 3 :2.4-5.0; and/or (Na) 2 O+K 2 O)/ZnO：2.6-4.3。
Further, T of the glass Unexposed-crystallization-380 nm Not less than 70%, preferably T Unexposed-crystallization-380 nm More preferably at least 87%, further preferably at the end T Unexposed-crystallization-380 nm ≥89％。
Further, [ nd ] of the glass Original glass -nd Unexposed-crystallization ]2930ppm or less, preferably after [ nd ] Original glass -nd Unexposed-crystallization ]≤710ppm。
Further, T of the glass Exposure-crystallization-440 nm ≥31％，T Exposure-crystallization-780 nm More than or equal to 73%, preferably the post sample T Exposure-crystallization-440 nm ≥45％，T Exposure-crystallization-780 nm More preferably not less than 77%, further preferably T Exposure-crystallization-440 nm ≥50％、T Exposure-crystallization-780 nm ≥82％。
Further, the refractive index modulation Deltand of the glass is 0 to 1500ppm, preferably after that Deltand is not less than 120ppm.
The second purpose of the invention is to protect a photo-thermal refraction glass preparation method, after fully and uniformly mixing the raw materials, melting the raw materials at 1350-1500 ℃ and carrying out atmosphere control, clarification and homogenization, and then cooling; pouring the molten glass into a mould for molding, and introducing circulating cooling air to ensure that the glass is not devitrified; and (3) placing the formed glass and the mold into an annealing furnace for heat preservation and annealing, and then powering off and cooling along with the furnace to obtain the transparent glass with high matrix stability and high refractive index modulation capability.
The third object of the invention is to protect the application of photo-thermal refractive glass for preparing the Bragg grating with high diffraction efficiency.
A fourth object of the invention is to protect a glass preform, made of the above glass.
A fifth object of the invention is to protect an optical element, made of the glass described above.
A sixth object of the invention is to protect an optical instrument, made of the glass described above.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention reasonably selects the component content of PTR glass by optimizing Sb 2 O 3 、SnO 2 Br component (ingredient) SiO of glass network former 2 The glass with high matrix stability, difficult phase separation, high optical transmittance, good crystallization resistance in a non-exposure area, more obvious refractive index difference between the exposed area and the non-exposure area after crystallization and stronger refractive index modulation capability is obtained by introducing the weight concentration ratio. The glass obtained by the invention is special glass with low optical loss and excellent photo-thermal refraction performance, and is favorable for preparing the high-diffraction-efficiency volume Bragg grating. The invention does not contain lead, cadmium, arsenic and other compounds, and the production process does not generate three wastes, thereby being environment-friendly.
2. The glass obtained by the invention has high matrix stability and is not easy to separate phases. The glass obtained by the invention has high optical transmittance in the wave band with the wavelength of 780nm and above of the alkali metal laser, reduces the optical loss of the PTR-based glass body Bragg grating device in the use process, reduces the temperature rise, and improves the working efficiency and the reliability of a laser system and equipment. Meanwhile, the glass has good crystallization resistance in a non-exposure area, can ensure that the non-exposure area and the exposure area have larger refractive index difference after crystallization treatment, and has excellent refractive index modulation capability at 588 nm.
3. The invention adjusts and controls Br component and SiO in glass formula component 2 The weight percentage of the components is combined with SnO 2 、SbO 3 The formula design of the components improves the optical loss of the glass sample and the refractive index modulation degree of the glass sample, and PTR glass with high optical transmittance and high refractive index modulation capability is obtained.
Detailed Description
The invention reasonably selects the component content of PTR glass: by optimizing Sb 2 O 3 SiO with glass network former 2 The weight concentration ratio is introduced, so that the transmittance reduction caused by the phase separation phenomenon of PTR glass in the heat treatment process is effectively improved; by optimizing SnO 2 SiO with glass network former 2 Introducing weight concentration proportion, regulating and controlling the stability of the glass substrate under the condition of no exposure induction, so that crystallization is inhibited in the crystallization process, and higher refractive index modulation capability can be realized; by optimizing and controlling Sb 2 O 3 、SnO 2 The weight concentration ratio of the glass fiber is improved effectively; siO formed by optimizing Br and glass network 2 The weight concentration ratio is introduced, and the optical transmittance of the glass substrate after exposure and nucleation is regulated so as to obtain low optical loss.
The content ranges and effects of the respective chemical components (ingredients) in the glass of the present invention will be described in detail below, and the content of each component is expressed in weight percent (wt%) with respect to the total weight of the glass, unless otherwise specified.
SiO 2 Is a glass-forming oxide, forms an irregular continuous network with structural units of silicon oxygen tetrahedra, and forms a skeleton of the optical glass. SiO (SiO) 2 Excessive content can lead to high viscosity of glass, so that melting temperature is high, melting is difficult, glass is difficult to form, and high-temperature melting leads to high volatilization of components of the glass, and particularly affects the content of a component F, br which is a volatile element in PTR glass. And SiO 2 When the content is too small, the glass is easy to crystallize and phase split, and the transmittance of the glass can be affected. Thus, siO 2 The content of (C) is in the range of 60.0 to 70.0%, preferably 61.0 to 68.0%, more preferably 61.0 to 67.6%.
ZnO is a glass network intermediate, and enters a glass network structure in [ ZnO4] tetrahedra respectively, so that network channels can be provided for the formation of NaF microcrystals. The proper amount of Zn element can reduce the expansion coefficient of glass and raise chemical stability and heat stability. However, excessive Zn addition results in a decrease in Na available for forming NaF crystallites, affecting the refractive index modulating ability of the glass. The ZnO content of the present invention is in the range of 4.0 to 8.0%, preferably 4.5 to 7.5%, more preferably 5.8 to 6.9%.
Al 2 O 3 As an intermediate of glass network, in [ AlO ] 4 ]Tetrahedra enter the glass network structure. Al (Al) 2 O 3 The introduction of the glass has the phase separation effect of inhibiting the glass in the forming and crystallization processes, and simultaneously can improve the strength and the hardness of the glass. And Al is 2 O 3 The presence of (2) increases the molding range of the glass in the three-dimensional phase diagram, enhances the chemical stability of the glass, and can improve the transparency of the glass. However, too much Al element incorporation results in a reduction of Na and F available for forming NaF crystallites, affecting the refractive index modulating ability of the glass. Therefore Al in the present invention 2 O 3 The content is in the range of 4.0 to 9.0%, preferably 4.5 to 8.0%, more preferably 4.6 to 6.8%.
Alkali metal oxide Na 2 O、K 2 O is an exosome of the glass network and is a crystallite-forming component. The introduction of the glass components can reduce the viscosity of the glass during high-temperature smelting, lower the smelting temperature of the glass, reduce the volatilization of the glass components and improve the stability of the volatile components F, br in the PTR glass. Na (Na) 2 O、K 2 Too much O can increase the devitrification and phase separation tendencies of the glass, induce a decrease in the transmittance of the glass, and decrease the chemical resistance of the glass. Too little tends to lower the crystallization tendency, which is disadvantageous in improving the refractive index modulating ability. In the present invention, na 2 O+K 2 The O content is in the range of 16.0 to 25.0%, preferably 16.5 to 23.5%, more preferably 16.6 to 23.2%.
Br is a component of PTR glass nucleation and also has the effect of reducing the high temperature and low viscosity of the glass and lowering the melting temperature. In addition, the addition of Br can reduce the solubility of F in the glass, so that the F which can be used for NaF microcrystal growth is increased, and the refractive index modulation capability of the glass is improved; however, too much Br results in easier phase separation during crystallization of the glass and lower transmittance. Accordingly, the Br content in the present invention is in the range of 0.5 to 2.0%, preferably 0.7 to 1.6%, more preferably 0.7 to 1.3%.
The more the content of F element is as the main component of NaF microcrystal formation, the more the refractive index modulation capability of the glass is improved. In addition, the introduction of F has the effect of reducing the high temperature and low viscosity of the glass and lowering the melting temperature. However, too much F element is introduced to easily cause crystallization and crystallization to be difficult to control, the grain size is excessively grown, and phase separation is easily caused in the crystallization process of glass, so that the absorption loss of the glass is increased. The content of F in the present invention is limited to 2.0 to 4.0%, preferably 2.3 to 3.1%, more preferably 2.4 to 3.1%.
Ag 2 O is a crystal nucleus agent of glass, and the more is introduced, the more Ag is easily formed in the exposure process 0 Is beneficial to improving the photosensitivity of the glass. However, excessive introduction can lead to crystallization in the unexposed area of the glass, and increase the absorption loss of the glass. In the present invention, ag 2 The O content is in the range of 0.010 to 0.060%, preferably 0.020 to 0.040%, more preferably 0.024 to 0.040%.
Ce 3+ Is a photosensitive ion in glass, and Ce in the glass is in the ultraviolet light exposure process of 300-325 nm 3+ Is excited by photons to generate photoelectrons, which are formed by Ag + Ion capturing electrons to form silver atoms Ag 0 . Silver atom Ag during heat treatment 0 Nucleation of Ag 0 And (3) cluster crystal nuclei. Ce (Ce) 3+ The more the ions are introduced, the more the photosensitivity of the glass is improved, and more Ag is formed under the same exposure dose 0 . But too much is introduced due to Ce 3+ The intrinsic broadband absorption at 300-325 nm can make the absorption of the corresponding wave band too strong, and influence the exposure uniformity of the glass in depth in the grating writing process. Thus, in the present invention CeO 2 The content of the introduced material is 0.010 to 0.050%, preferably 0.022 to 0.036%.
SnO 2 、Sb 2 O 3 Are all sensitizers, and the introduction of the sensitizers can release electrons in the heat treatment process to inhibit Ag in the heat treatment process 0 To Ag + The rate of transition favors nucleation. But Sn is 4+ With Sb 5+ Ions can react with Ag during exposure + Ions compete for electrons, resulting in the formation of Ag 0 Atomic reduction results in reduced photosensitivity of the glass. Meanwhile, sn and Sb elements are excessively introduced to form defects, so that the temperature rise of the glass is accelerated during working, and the working stability of the glass is influenced. Therefore in the present inventionLimited SnO 2 The content is 0.00 to 0.10%, preferably 0.00 to 0.08%, more preferably 0 to 0.05%. Sb (Sb) 2 O 3 The content is limited to 0.00 to 0.40%, preferably 0.00 to 0.35%, more preferably 0.1 to 0.32%.
The inventor of the present invention has repeatedly tested and studied:
regulation of Sb 2 O 3 Additive amount of glass network former SiO 2 By increasing the weight ratio of Sb 2 O 3 /SiO 2 Proportion of sample T after crystallization Unexposed-crystallization-380 nm Gradually increasing, meaning that its optical loss due to phase separation is reduced and the resistance to phase separation of the glass matrix is increased. But Sb 2 O 3 /SiO 2 Too high a ratio results in a decrease in the degree of modulation of the refractive index of the glass, while an increase in the content thereof increases the light absorption of Sb ions in the glass. Sb in the present invention 2 O 3 /SiO 2 The ratio is limited to 0-46 multiplied by 10 -4 Preferably 19 to 46X 10 -4 More preferably 21 to 46. Within the limits of the Sb/Si of the invention, glass T is obtained Unexposed-crystallization-380 nm More than or equal to 70%, preferably T Unexposed-crystallization-380 nm More preferably at least 87%, further preferably at the end T Unexposed-crystallization-380 nm ≥89％。
Regulating and controlling SnO 2 Additive amount of glass network former SiO 2 Weight ratio by increasing SnO 2 /SiO 2 Proportion, after crystallization of the sample [ nd ] Original glass -nd Unexposed-crystallization ]The anti-crystallization capability of the corresponding unexposed area is enhanced and then reduced firstly, and SnO is reduced firstly 2 /SiO 2 Limited to 0 to 11 multiplied by 10 -4 Preferably in the range of 4 to 6X 10 -4 . SnO in the present invention 2 /SiO 2 Within a limited range, glass [ nd ] Original glass -nd Unexposed-crystallization ]2930ppm or less, preferably after [ nd ] Original glass -nd Unexposed-crystallization ]≤710ppm。
SiO of glass network forming body is formed by regulating and controlling Br addition amount 2 The weight ratio of (c) will affect its transmittance and refractive index modulation: br/SiO 2 An increase in the ratio will lead to glassThe transmittance of the glass gradually decreases, and simultaneously Br/SiO 2 An increase in the ratio will result in an increase followed by a decrease in the refractive index modulation Δnd of the glass of the determined matrix component. Br/SiO in the present invention 2 The ratio is limited to 11-24×10 -3 Preferably 11 to 20X 10 -3 More preferably 11 to 15X 10 -3 . In the present invention Br/SiO 2 Within a limited range, glass T is obtained Exposure-crystallization-440 nm ≥31％、T Exposure-crystallization-780 nm More than or equal to 73%, preferably the post sample T Exposure-crystallization-440 nm ≥45％、T Exposure-crystallization-780 nm More preferably not less than 77%, further preferably T Exposure-crystallization-440 nm ≥50％、T Exposure-crystallization-780 nm ≥82％。
The invention is realized by controlling (Na 2 O+K 2 O)/Al 2 O 3 In the range of 2.4-5.0, the glass transmittance and the refractive index modulation degree are obviously controlled, the glass transmittance is deteriorated due to the excessive proportion, and the refractive index modulation performance is poor due to the excessive proportion; by controlling (Na 2 O+K 2 O)/ZnO is in the range of 2.6 to 4.3, and an increase in the ratio will cause deterioration of the glass transmittance, and a decrease in the ratio will cause deterioration of the refractive index modulation performance.
Within the range of the components and the synergistic relationship of the invention, the refractive index modulation Deltand of 0-1500 ppm of glass can be obtained, and the Deltand is preferably more than or equal to 120ppm.
The glass preparation method comprises the following steps: selecting a glass formula, preparing raw materials (such as oxide, fluoride, carbonate, nitrate and the like) according to the proportion of glass components (components), fully and uniformly mixing, adding the raw materials into a platinum crucible, melting the raw materials at 1350-1500 ℃, controlling the atmosphere (such as nitrogen, carbon dioxide and the like), clarifying, homogenizing and cooling; pouring the molten glass into a preheating mould for molding, and introducing circulating cooling air to ensure that the glass is not devitrified; and (3) placing the formed glass and a metal mold into an annealing furnace for heat preservation and annealing, and then powering off and cooling along with the furnace to obtain the transparent glass with high matrix stability and high refractive index modulation capability. Those skilled in the art can appropriately select the raw materials, the process methods, and the process parameters according to actual needs.
[ glass preform and optical element ]
The optical glass thus produced may be used to produce a glass preform by using, for example, polishing, reheat press molding, precision press molding, or other press molding means. That is, the glass preform may be produced by mechanically working the optical glass by grinding or polishing, or by producing a preform for press molding from the optical glass, and then performing the polishing after the hot press molding, or by performing the precision press molding on the preform produced by the polishing.
The means for producing the glass preform is not limited to the above-described means. As described above, the optical glass of the present invention is useful for various optical elements and optical designs, and among them, it is particularly preferable to form a preform from the optical glass of the present invention, and use the preform for performing hot press molding, precision press molding, and the like to produce optical elements such as lenses and prisms.
The glass preform and the optical element of the present invention are each formed of the optical glass of the present invention described above. The glass preform of the present invention has excellent characteristics possessed by an optical glass; the optical element of the present invention has excellent characteristics of optical glass, and can provide various optical elements such as lenses and prisms having high optical value.
Examples of the lens include various lenses such as a concave meniscus lens, a convex meniscus lens, a biconvex lens, a biconcave lens, a plano-convex lens, and a plano-concave lens, each of which has a spherical or aspherical lens surface.
[ optical instruments or devices ]
The optical element formed by the optical glass can be used for manufacturing optical instruments or devices such as diffraction optical instruments or devices, structural optical instruments or devices, high-resolution high-speed holographic recording instruments or devices and the like. The performance index method of the invention is as follows:
[ optical transmittance ]
The light transmittance is referred to herein as external transmittance, abbreviated as transmittance.
The glass was produced into a sheet sample and subjected to surface parallel mirror polishing, and the transmittance of the glass at 380nm, 440nm and 780nm was measured by using a Hitachi U-41000-shaped spectrophotometer. The testing method is based on the national standard: colorless optical glass test method part 12: transmittance in the spectrum; standard number: GB/T7962.12-2010
[ refractive index ]
The refractive index nd at 587.6nm of the glass was measured here using a V prism refractometer. The testing method is based on the national standard: colorless optical glass test method part 1: refractive index and dispersion coefficient; standard number: GB/T7962.1-2010.
The comparison of glass performance indexes relates to exposure and heat treatment operations, the exposure treatment time is controlled to be 3min, the crystallization treatment process is unified and consistent, the treatment temperature is 460-600 ℃, the treatment time is limited and consistent, and the time range is 0-2 h.
In evaluating the phase separation of glass after heat treatment, the transmittance T at 380nm after crystallization of an unexposed glass sample is used Unexposed-crystallization-380 nm For evaluation purposes, glass phase separation will result in a decrease in this transmittance.
In evaluating the crystallization resistance of the glass in the non-exposed area after heat treatment, the refractive index difference [ nd ] between the refractive index of the original glass and the refractive index of the non-exposed glass after crystallization Original glass -nd Unexposed-crystallization ]For evaluation, more devitrification after crystallization of glass will lead to [ nd Original glass -nd Unexposed-crystallization ]The larger the value.
In evaluating the optical loss of the glass, 440nm (T) Exposure-crystallization-440 nm ) And 780nm (T) Exposure-crystallization-780 nm ) Transmittance at the site was used as an evaluation method. The intrinsic absorption band at 440nm, which corresponds to nucleation during the glass heat treatment, cannot be completely eliminated, but can be controlled by the formulation components and process. The 780nm is the wavelength of a common alkali metal laser, and is the application wave band of glass.
In evaluating the refractive index modulation ability of the glass, the refractive index after crystallization of the unexposed glass and the refractive index after crystallization of the exposed glass are usedThe difference Δnd, i.e. Δnd=nd Unexposed light -nd Exposure to light For the evaluation mode, the larger Δnd is, the stronger the refractive index modulation capability is.
Specific examples of glasses according to the invention are shown in tables 1 to 4 below.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
/>
The above is an embodiment exemplified in this example, but this example is not limited to the above-described alternative embodiments, and a person skilled in the art may obtain various other embodiments by any combination of the above-described embodiments, and any person may obtain various other embodiments in the light of this example. The above detailed description should not be construed as limiting the scope of the present embodiments, which is defined in the claims and the description may be used to interpret the claims.
Claims (23)
1. A photo-thermal fold glass, characterized in that: the components of the composition are as follows in percentage by weight: siO (SiO) 2 ：60.0～70.0％；ZnO：4.0～8.0％；Al 2 O 3 ：4.0～9.0％；Br：0.5～2％；F：2.0～4.0％；Ag 2 O：0.010～0.060％；CeO 2 ：0.010～0.050％；SnO 2 ：0.00～0.10％；Sb 2 O 3 ：0.00～0.40％；Na 2 O+K 2 O:16.0 to 25.0 percent; wherein Br/SiO 2 ：11～24×10 -3 ，SnO 2 /SiO 2 ：3.6～11×10 -4 ，Sb 2 O 3 /SiO 2 ：15～46×10 -4 。
2. A photo-thermal fold glass, characterized in that: the components of the composition are represented by weight percent: siO (SiO) 2 ：60.0～70.0％；ZnO：4.0～8.0％；Al 2 O 3 ：4.0～9.0％；Br：0.5～2％；F：2.0～4.0％；Ag 2 O：0.010～0.060％；CeO 2 ：0.010～0.050％；SnO 2 ：0.00～0.10％；Sb 2 O 3 ：0.00～0.40％；Na 2 O+K 2 O:16.0 to 25.0 percent; wherein Br/SiO 2 ：11～24×10 -3 ，SnO 2 /SiO 2 ：3.6～11×10 -4 ，Sb 2 O 3 /SiO 2 ：15～46×10 -4 。
3. The photothermal refractive glass according to claim 1 or 2, comprising the following components in percentage by weight: siO (SiO) 2 ：61.0～68.0％；ZnO：4.5～7.5％；Al 2 O 3 ：4.5～8.0％；Br：0.7～1.6％；F：2.3～3.1％；Ag 2 O：0.020～0.040％；CeO 2 ：0.022～0.036％；SnO 2 ：0.00～0.08％；Sb 2 O 3 ：0.00～0.35％；
Na 2 O+K 2 O：16.5～23.5％；Br/SiO 2 ：11～20×10 -3 。
4. A photo-thermal refractive glass according to claim 3, wherein the composition is expressed in weight percent: siO (SiO) 2 ：61.0～67.6％；ZnO：5.8～6.9％；Al 2 O 3 ：4.6～6.8％；Br：0.7～1.3％；F：2.4～3.1％；Ag 2 O：0.024～0.040％；SnO 2 ：0～0.05％；Sb 2 O 3 ：0.1～0.32％；Na 2 O+K 2 O：16.6～23.2％；
Br/SiO 2 ：11～15×10 -3 。
5. A photo-thermal refraction glass according to claim 1 or 2, wherein the composition comprises SnO in weight percent 2 /SiO 2 ：4～11×10 -4 The method comprises the steps of carrying out a first treatment on the surface of the And/or Sb 2 O 3 /SiO 2 ：19～46×10 -4 。
6. The photo-thermal glass as defined in claim 5, wherein the composition is SnO 2 /SiO 2 ：4～6.5×10 -4 The method comprises the steps of carrying out a first treatment on the surface of the And/or Sb 2 O 3 /SiO 2 ：
21～46×10 -4 。
7. A photothermal refractive index glass according to claim 1 or 2, wherein: the components are expressed in weight percent, (Na) 2 O+K 2 O)/Al 2 O 3 :2.4-5.0; and/or
(Na 2 O+K 2 O)/ZnO：2.6-4.3。
8. A photothermal refractive index glass according to claim 1 or 2, wherein: the glass isT of (2) Unexposed-crystallization-380 nm ≥70％。
9. The photo-thermal fold glass according to claim 8, wherein: t of the glass Unexposed-crystallization-380 nm ≥87％。
10. The photo-thermal fold glass according to claim 9, wherein: t of the glass Unexposed-crystallization-380 nm ≥89％。
11. A photothermal refractive index glass according to claim 1 or 2, wherein: nd of the glass Original glass -nd Unexposed-crystallization ]≤2930ppm。
12. The photo-thermal fold glass according to claim 11, wherein: nd of the glass Original glass -nd Unexposed-crystallization ]≤710ppm。
13. A photothermal refractive index glass according to claim 1 or 2, wherein: t of the glass Exposure-crystallization-440 nm ≥31％，T Exposure-crystallization-780 nm ≥73％。
14. The photo-thermal fold glass according to claim 13, wherein: t of the glass Exposure-crystallization-440 nm ≥45％，T Exposure-crystallization-780 nm ≥77％。
15. The photo-thermal fold glass according to claim 14, wherein: t of the glass Exposure-crystallization-440 nm ≥50％、T Exposure-crystallization-780 nm ≥82％。
16. A photothermal refractive index glass according to claim 1 or 2, wherein: the refractive index modulation Deltand of the glass is 0-1500 ppm.
17. The photo-thermal fold glass according to claim 16, wherein: the refractive index modulation degree Delnd of the glass is more than or equal to 120ppm.
18. The method for producing a photo-thermal folded glass according to any one of claims 1 to 17, wherein: after fully and uniformly mixing the raw materials, melting the raw materials at 1350-1500 ℃, performing atmosphere control, clarifying, homogenizing and cooling; pouring the molten glass into a mould for molding, and introducing circulating cooling air to ensure that the glass is not devitrified; and (3) placing the formed glass and the mold into an annealing furnace for heat preservation and annealing, and then powering off and cooling along with the furnace to obtain the transparent glass with high matrix stability and high refractive index modulation capability.
19. Use of a photothermal refractive index glass according to any of claims 1 to 17, wherein: for use in the fabrication of diffractive optical devices.
20. The use of a photothermal refractive index glass according to claim 19, wherein: is used for manufacturing the high diffraction efficiency volume Bragg grating.
21. A glass preform, characterized in that: a photo-thermal refractive glass according to any one of claims 1 to 17.
22. An optical element, characterized in that: use of a photothermal refractive glass according to any of claims 1 to 17 or use of a glass preform according to claim 21.
23. An optical instrument, characterized in that: use of a photothermal refractive glass according to any of claims 1-17 or use of an optical element according to claim 22.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211062625.1A CN115432922B (en) | 2022-08-31 | 2022-08-31 | Photo-thermal refraction glass and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211062625.1A CN115432922B (en) | 2022-08-31 | 2022-08-31 | Photo-thermal refraction glass and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115432922A CN115432922A (en) | 2022-12-06 |
| CN115432922B true CN115432922B (en) | 2023-09-19 |
Family
ID=84244814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211062625.1A Active CN115432922B (en) | 2022-08-31 | 2022-08-31 | Photo-thermal refraction glass and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115432922B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8455157B1 (en) * | 2007-04-26 | 2013-06-04 | Pd-Ld, Inc. | Methods for improving performance of holographic glasses |
| CN103592713A (en) * | 2013-11-29 | 2014-02-19 | 苏州大学 | Sidelobe-free angle-selection laser filter |
| CN108821569A (en) * | 2018-04-13 | 2018-11-16 | 苏州大学 | Laser holographic recording glass, diffraction optical device or hologram pattern product and preparation method |
| CN109052968A (en) * | 2018-09-11 | 2018-12-21 | 中国科学院西安光学精密机械研究所 | A kind of rare earth ion doped photo-thermal is quick to sell off laser glass ceramics and preparation method thereof |
| CN109704575A (en) * | 2019-03-11 | 2019-05-03 | 江苏师范大学 | A kind of photo-thermal is quick to sell off middle infrared glass and preparation method thereof |
| WO2020165448A1 (en) * | 2019-02-15 | 2020-08-20 | Université D'aix-Marseille | Optical metasurfaces, and associated manufacturing methods and systems |
-
2022
- 2022-08-31 CN CN202211062625.1A patent/CN115432922B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8455157B1 (en) * | 2007-04-26 | 2013-06-04 | Pd-Ld, Inc. | Methods for improving performance of holographic glasses |
| CN103592713A (en) * | 2013-11-29 | 2014-02-19 | 苏州大学 | Sidelobe-free angle-selection laser filter |
| CN108821569A (en) * | 2018-04-13 | 2018-11-16 | 苏州大学 | Laser holographic recording glass, diffraction optical device or hologram pattern product and preparation method |
| CN109052968A (en) * | 2018-09-11 | 2018-12-21 | 中国科学院西安光学精密机械研究所 | A kind of rare earth ion doped photo-thermal is quick to sell off laser glass ceramics and preparation method thereof |
| WO2020165448A1 (en) * | 2019-02-15 | 2020-08-20 | Université D'aix-Marseille | Optical metasurfaces, and associated manufacturing methods and systems |
| CN109704575A (en) * | 2019-03-11 | 2019-05-03 | 江苏师范大学 | A kind of photo-thermal is quick to sell off middle infrared glass and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Influence of glass composition on the refractive index change upon photothermoinduced crystallization;N.V.Nikonorov et al.;Glass Physics and Chemistry;第27卷(第3期);第241-249页 * |
| SiO2-Al2O3-ZnO-Na2O(F,Br)体系光热折变玻璃的析晶机理研究;徐子威等;光子学报;第49卷(第07期);全文 * |
| 曝光剂量与体布喇格光栅衍射特性的研究;熊宝星;张桂菊;邹快盛;;光子学报(第07期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115432922A (en) | 2022-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4589297B2 (en) | Optical glass | |
| CN108821569B (en) | Laser holographic recording glass, diffraction optical device or holographic pattern product and preparation method | |
| JP2022027829A (en) | Optical glass and optical element | |
| US6339033B2 (en) | Silica glass having superior durability against excimer laser beams and method for manufacturing the same | |
| Ehrt et al. | Radiation effects in glasses | |
| US7312170B2 (en) | Optical synthetic quartz glass and method for producing the same | |
| JP5349721B2 (en) | Optical glass with small refractive index change by light irradiation | |
| CN106746613A (en) | Optical glass | |
| JPH0388742A (en) | Synthetic silica glass optical body and production therefor | |
| CN115432922B (en) | Photo-thermal refraction glass and preparation method thereof | |
| DE112004002579B4 (en) | Photorefractive glass and optical elements made of it | |
| WO2022048335A1 (en) | Optical glass and optical element | |
| CN115403267B (en) | Photo-thermal refraction glass and preparation method thereof | |
| JPH03109233A (en) | Synthetic silica glass optical body for ultraviolet laser beam and its production | |
| CN115417597B (en) | Photothermographic variable glass with high transition temperature and preparation method thereof | |
| CN115572065B (en) | Photothermal sensitive refractive glass with low absorption loss and preparation method thereof | |
| CN115572063B (en) | Photothermographic variable glass with low melting temperature and preparation method thereof | |
| CN104761147B (en) | A kind of extraordinary flint glass and preparation method thereof | |
| JP2015157716A (en) | Optical glass, preform material, and optical element | |
| JP2011251903A (en) | Optical glass suffering little change in refractive index by radiation of light | |
| CN112028473A (en) | Optical glass for precision mould pressing | |
| JPH0912323A (en) | Quartz glass member suppressed from becoming dense due to irradiation of uv ray | |
| US7265070B2 (en) | Synthetic silica glass optical material having high resistance to optically induced index change | |
| JP2019182716A (en) | Optical glass and optical element | |
| CN114853338A (en) | Low melting point glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |