CN108821569B - Laser holographic recording glass, diffraction optical device or holographic pattern product and preparation method - Google Patents
Laser holographic recording glass, diffraction optical device or holographic pattern product and preparation method Download PDFInfo
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- CN108821569B CN108821569B CN201810333771.0A CN201810333771A CN108821569B CN 108821569 B CN108821569 B CN 108821569B CN 201810333771 A CN201810333771 A CN 201810333771A CN 108821569 B CN108821569 B CN 108821569B
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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
- 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
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
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- 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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/18—Diffraction gratings
- G02B5/1847—Manufacturing methods
- G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
Abstract
The invention discloses laser holographic recording glass, a diffraction optical device or a holographic pattern product and a preparation method thereof, wherein the laser holographic recording glass comprises the following components in parts by weight: SiO 2255-65 parts of Na212-20 parts of O (ZnO + Al)2O3) 8-13 parts of NaF, 4-8 parts of (KBr + AgBr + NaBr + NaCl + KCl) 0.2-5 parts of (BaO + La)2O3+B2O3) 2-6 parts of Ag20.01-1 part of O, (Sb)2O3+SnO2)0 to 1 part of CeO20.01-1 part. The laser holographic recording glass has low melting temperature, can be clarified and homogenized at 1380-1420 ℃, has a heat treatment temperature lower than the softening temperature of the glass, and greatly improves the yield of devices; meanwhile, the laser holographic recording glass takes silver halide as a crystal nucleus agent, and the damage threshold is also obviously improved.
Description
Technical Field
The invention relates to the technical field of glass, in particular to laser holographic recording glass, a diffraction optical device or a holographic pattern product and a preparation method thereof.
Background
The laser holographic recording glass is a glass with Photo-thermal Refractive (PTR) effect, and the glass contains photosensitive factor (Ce)3+、Ag+) The phase change of the glass can be generated after ultraviolet exposure and heat treatment, so that the refractive index of the glass in an exposed area is changed, and the refractive index difference (delta n) between tens of ppm and hundreds of ppm and an unexposed area exist.
The VBG diffraction optical element based on the laser holographic recording glass has important application prospects in advanced laser technologies such as compression and broadening of laser pulses, angle selection near-field filtering, semiconductor laser output spectrum stabilization, laser output mode selection, holographic recording and the like.
The VBG with high diffraction efficiency can greatly improve the performance of the laser and the system thereof, and has important significance in researching how to improve the diffraction efficiency of the volume grating and preparing the VBG with high efficiency. The diffraction efficiency of VBG is affected by parameters such as the refractive index modulation degree (Δ n) of the grating, the grating thickness (d), the absorption characteristic (α) of the laser hologram recording glass for the exposure wavelength, and the uniformity of the laser hologram recording glass, which are related to the characteristics of the laser hologram recording glass itself.
Internationally, Glebov et al, university of Florida, USA, prepares PTR glass with excellent performance by optimizing PTR glass formula, and successfully applies to VBG preparation, and the caliber of VBG which can be prepared at present can reach 100 mm.
In China, Suzhou university researches the preparation characteristics of the volume grating from the aspects of PTR glass components, heat treatment process and the like, and the PTR glass is firstly developed in 2012 and used for manufacturing the high-efficiency volume grating; in 2013, Beijing industry university studied the variable wavelength readout characteristics and laser irradiation stability of the volume grating; in 2015, PTR glass is prepared by Chinese building material science research institute, and the influence rule of ultraviolet exposure dose on refractive index modulation degree is obtained.
In 2003, the composition of the PTR glass invented by Efimov et al, USA, was as follows: 13.6Na2O-5.2ZnO-2.3Al2O3-72.3SiO2-3.7NaF-1.5KBr-1.2AlF3(mol%) while being doped with 0.01Ag2O-0.01CeO2-0.001SnO2-0.03Sb2O3(mol%) (U.S. Pat. No. US6,586,141B1). The glass is microcrystalline glass, silver is used as a crystal nucleus agent, controlled crystallization is realized in an ultraviolet exposure mode, and the holographic recording principle is as follows: the photo-thermal first-stage glass sample is irradiated by near ultraviolet light, Ce3+Is oxidized into Ce4+An electron is released, the released electron is captured by silver ion, and the silver ion is changed into Ag0(ii) a In the second stage, silver atoms are rapidly diffused and accumulated near the nucleation temperature (450-500 ℃) to form tiny silver crystals, and then a large number of silver nuclei are generated; the third stage, heating to 500-550 ℃, and inducing the silver core particles to obtain F in the glass-Ions and Na+Ions are gathered to silver nuclei to form NaF crystals, the number of crystal nuclei in an exposure area is maximum, and the crystalsThe NaF crystal volume fraction in the exposed area after the crystallization is the highest, so the refractive index change is about large. The refractive index of the NaF crystal was 1.32, and the refractive index of the unexposed area glass was 1.49, and holographic recording was achieved by controlling the change in refractive index formed by exposure.
The laser holographic recording glass invented by Efimov et al in America has high melting temperature of 1450-1500 ℃, a silicon-molybdenum rod melting furnace is required for heating, and the glass melting cost is high; meanwhile, the heat treatment temperature range is 480-580 ℃, the temperature exceeds the softening temperature point of the glass, the glass is easy to deform during the preparation of the device, and the control is not easy, so that the yield of the device is low. The traditional holographic recording glass PTR glass takes silver aggregated into nano silver particles as a crystal nucleating agent, and after the holographic recording glass PTR glass is prepared into a holographic optical element, the silver particles exist in the glass element, so that the damage threshold of the prepared device is low.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide laser holographic recording glass, a diffraction optical device or a holographic pattern product and a preparation method thereof, and aims to solve the problems that the melting cost is high due to high melting temperature of the existing laser holographic recording glass, the heat treatment temperature exceeds the softening temperature point of the glass, the glass is easy to deform when a device is prepared, the yield of the device is low, and the damage threshold of the device prepared by the traditional holographic recording glass is low.
The technical scheme of the invention is as follows:
the invention provides laser holographic recording glass which comprises the following components in parts by weight: SiO 2255-65 parts of Na212-20 parts of O (ZnO + Al)2O3) 8-13 parts of NaF, 4-8 parts of (KBr + AgBr + NaBr + NaCl + KCl) 0.2-5 parts of (BaO + La)2O3+B2O3) 2-6 parts of Ag20.01-1 part of O, (Sb)2O3+SnO2)0 to 1 part of CeO20.01-1 part.
Preferably, the laser holographic recording glass comprises the following components in parts by weight: SiO 2260 to 62 parts of Na215-18 parts of O, 3-5 parts of ZnO and Al2O35-9 parts of NaF 4-6 parts of KBr 3-5 parts of B2O32-5 parts of Ag20.05 to 0.07 part of O, Sb2O30.1 to 0.3 part of CeO20.03 to 0.05 portion.
More preferably, the laser holographic recording glass comprises the following components in parts by weight: SiO 2261.6 parts of Na215 portions of O, 4 portions of ZnO and Al2O38 portions of NaF 4.5 portions, KBr 3.5 portions, B2O33.2 parts of Ag20.07 part of O, Sb2O30.1 part of CeO20.03 part.
The invention also provides a preparation method of the laser holographic recording glass, wherein the preparation method of the laser holographic recording glass comprises the following steps:
accurately weighing the raw materials according to the proportion;
finely grinding the raw materials in a mortar to enable the raw materials to be fully and uniformly mixed, and gradually adding the raw materials into a quartz crucible at 1220-1240 ℃ to enable the mixture to be melted into a glass state to obtain glass state clinker;
pouring the glassy clinker into a platinum crucible in batches at 1350-1360 ℃, stirring to clarify and homogenize glass to obtain a high-temperature melt, wherein the melting temperature is 1380-1420 ℃, and the melting time is 5-12 h;
transferring the high-temperature melt into a copper mold at the temperature of 1290-1310 ℃, transferring the high-temperature melt into an annealing furnace, preserving the heat at the temperature of 450-470 ℃ for 2-6 hours, and finally cooling to room temperature at a constant speed to obtain the laser holographic recording glass.
The preparation method of the laser holographic recording glass comprises the steps of cooling to room temperature at a cooling rate of 4-6 ℃/h, and obtaining the laser holographic recording glass through optical cold processing technologies such as cutting, coarse grinding, fine grinding and polishing according to the required size specification, wherein the laser holographic recording glass can be used for manufacturing of subsequent diffraction devices or recording of holographic patterns.
The invention also provides a diffraction optical device or a holographic pattern product, wherein the laser holographic recording glass is made of the laser holographic recording glass.
The present invention also provides a method of manufacturing a diffractive optical element or a holographic pattern article as described above, wherein the method of manufacturing the diffractive optical element or the holographic pattern article comprises the steps of:
exposing the laser holographic recording glass, and writing interference fringes according to a designed grating period;
and carrying out heat treatment on the exposed laser holographic recording glass to generate permanent refractive index change so as to obtain the diffraction optical device or the holographic pattern product, wherein the heat treatment process comprises nucleation and crystallization, the nucleation temperature is 430-530 ℃, and the crystallization temperature is 510-540 ℃.
The preparation method of the diffraction optical device or the holographic pattern product comprises the following steps of exposing laser holographic recording glass in a near ultraviolet light source interference exposure or femtosecond laser light source direct writing mode; for the uniform period volume Bragg grating, exposing in a mode of double plane wave beam interference; and for the chirped volume Bragg grating, the exposure is carried out in a mode of interference of plane waves and spherical waves.
Has the advantages that: the invention provides laser holographic recording glass, a diffraction optical device or a holographic pattern product and a preparation method thereof, the laser holographic recording glass has low melting temperature, can be clarified and homogenized at 1380-1420 ℃, can be melted by using a common silicon carbide rod electric furnace, has heat treatment temperature lower than the softening temperature of glass, and greatly improves the yield of devices; meanwhile, the laser holographic recording glass takes silver halide as a crystal nucleus agent, the silver halide can be decomposed by secondary illumination treatment in the later period, and the particle size of silver in the obtained product is greatly smaller than that of the conventional PTR glass, so that the damage threshold can be obviously improved.
Detailed Description
The invention provides laser holographic recording glass, a diffraction optical device or a holographic pattern product and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The laser holographic recording glass provided by the preferred embodiment of the invention comprises the following components in parts by weight: SiO 2255-65 parts of Na212-20 parts of O (ZnO + Al)2O3) 8-13 parts of NaF, 4-8 parts of (KBr + AgBr + NaBr + NaCl + KCl) 0.2-5 parts of (BaO + La)2O3+B2O3) 2-6 parts of Ag20.01-1 part of O, (Sb)2O3+SnO2)0 to 1 part of CeO20.01-1 part.
Further, SiO2Is the main oxide of the base glass, with silicon-oxygen tetrahedron [ SiO ]2]The structural units of (a) are connected with each other to form an irregular continuous network body which is a framework of the base glass. SiO 22An increase in the content is advantageous for improving the mechanical strength of the glass, but the glass becomes difficult to melt when the content is too high. In this example, SiO2The content of (b) is 55 to 65 parts, and may be, for example, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, or the like.
Further, Na2O acts as a cosolvent and a clarifying agent, with NaNO3Or Na2CO3Is introduced in the form of (1). Na (Na)2O is an extranet oxide of the basic glass network which provides Na ions+In the cavities of the network, free oxygen can be provided2]The O/Si ratio in the network body is increased, and silicon-oxygen bonds are broken, so that the viscosity of the glass is reduced, the glass is easy to melt, and the clarification of the glass is facilitated. But Na2The amount of O to be introduced should not be excessive, which would otherwise result in an increase in the thermal expansion coefficient of the glass and a decrease in the thermal, chemical and mechanical strength of the glass. In this example, Na2The content of O is 12 to 20 parts, and for example, 12 parts, 15 parts, 17 parts, 18 parts, 20 parts and the like can be mentioned.
Further, ZnO and Al2O3The introduction of (A) is to reduce the devitrification tendency of the glass, to improve the chemical stability, thermal stability and mechanical strength of the glass, and to reduce the thermal expansion coefficient of the glass. ZnO is an intermediate oxide, in general, octahedral with zinc oxideBody [ ZnO ]6]As an external oxide of the network, when the free oxygen in the glass is sufficient, a zinc-oxygen tetrahedron [ ZnO ] can be formed4]And enter the structural network of the glass, so that the structure of the glass is more stable. Al (Al)2O3Also an intermediate oxide, has two coordination states in the glass, [ AlO ]4]And [ AlO ]6]. When the free oxygen is too much, [ AlO ]4]If the free oxygen is insufficient, [ AlO ] is used6]Are present. When in the high coordination state, the glass has a higher refractive index and a smaller molecular volume; when it is in a low coordination state, the refractive index and density of the glass are reduced. In this example, ZnO + Al2O3The content of (b) is 8 to 13 parts, and may be, for example, 8 parts, 10 parts, 12 parts, 13 parts, or the like.
Further, NaF is a glass light control crystallization component. The NaF content cannot be too low, which would result in too low a refractive index modulation obtained after exposure heat treatment; the NaF content should not be too high, otherwise the glass will tend to crystallize during the manufacturing stage. In the present embodiment, the amount of NaF is 4 to 8 parts, and may be, for example, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, or the like.
Further, the nucleating agent AgBr/AgCl is formed by AgNO3Or in the form of AgCl + halides. Wherein, Ag2O in photo-thermal treatment process, Ag2The silver ion part provided by O is reduced into silver atoms, halogen ions are oxidized into halogen atoms, and the silver atoms and the halogen atoms are subjected to chemical reaction together to generate silver halide micelles in the heat treatment process of the glass after illumination. In this embodiment, the content of (KBr + AgBr + NaBr + NaCl + KCl) is 0.2-5 parts, Ag2The content of O is 0.01-1 part. For example, (KBr + AgBr + NaBr + NaCl + KCl) can be 0.2 parts, 0.8 parts, 1 part, 3 parts, 5 parts, etc., Ag2O may be 0.01 part, 0.1 part, 0.5 part, 1 part, or the like.
Further, the barium oxide and the lanthanum oxide are introduced. BaO is also a network exo-oxide that can increase the refractive index, density, gloss and chemical stability of the glass. A small amount of BaO accelerates the melting of the glass, and when the amount is too high, the glass is difficult to clarify during the melting process. GlassThe addition of a proper amount of BaO in the glass can improve the capability of absorbing exposure. La2O3The chemical stability of the glass can be improved. B is2O3Can be used as a glass forming body to partially replace SiO2And the melting temperature of the glass is reduced under the condition of not influencing the overall performance of the glass. In this example, (BaO + La)2O3+B2O3) The content of (b) is 2 to 6 parts, and may be, for example, 2 parts, 4 parts, 5 parts, 6 parts, or the like.
Further, in order to easily remove bubbles in the glass during the preparation of the holographic glass, an appropriate amount of Sb may be introduced into the glass2O3Or SnO2，Sb2O3Absorbing oxygen released by decomposing nitrate in the raw material into Sb in the temperature rise process of 600-1200 DEG C2O5At a clarifying temperature of 1380-1420 ℃ in the glass2、Sb2O5Or SnO2Decomposing to release oxygen for clarifying the glass liquid and eliminating bubbles, wherein the reaction process is as follows:
in the present embodiment, (Sb)2O3+SnO2) The content of (b) is 0 to 1 part, and may be, for example, 0 part, 0.3 part, 0.6 part, 1 part, or the like.
Further, the present invention introduces a small amount of CeO2Mainly acts as a photosensitizing agent which provides part of the cerium ions in the trivalent state Ce3+In the form of Ce3+Under the condition of ultraviolet illumination, the silver ion is ionized to release an electron, and the electron and the silver ion Ag+The binding can promote the photosensitive reduction process of silver ions. In this example, CeO2The content of (B) is 0.01 to 1 part, and may be, for example, 0.01 part, 0.03 part, 0.05 part, 0.1 part, 1 part, or the like.
The laser holographic recording glass has the following process and performance advantages: 1) the glass melting temperature is low, clarification and homogenization can be realized at 1380-1420 ℃, and melting can be completed by using a common silicon carbide rod electric furnace; 2) the holographic recording heat treatment temperature is lower than the glass softening temperature, so that the yield of the device is greatly improved; 3) according to the invention, silver halide is used as a crystal nucleus agent, the silver halide can be decomposed by secondary illumination treatment in the later stage, and the particle size of silver in the obtained product is greatly smaller than that of the conventional PTR glass, so that the damage threshold can be obviously improved.
Preferably, the laser holographic recording glass comprises the following components in parts by weight: SiO 2260-62 parts of Na215-18 parts of O, 3-5 parts of ZnO and Al2O35-9 parts of NaF 4-6 parts of KBr 3-5 parts of B2O32-5 parts of Ag20.05 to 0.07 part of O, Sb2O30.1 to 0.3 part of CeO20.03～005 parts. Wherein, the content of ZnO can be 3 parts, 4 parts, 5 parts and the like, Al2O3The content of (B) may be 5 parts, 8 parts, 9 parts, etc., the content of KBr may be 3 parts, 4 parts, 5 parts, etc., B2O3The content of (B) can be 2 parts, 4 parts, 5 parts and the like, Sb2O3The content of (b) may be 0.1 part, 0.2 part, 0.3 part, etc. The laser holographic recording glass adopting the optimized formula has the advantages of better process and performance.
More preferably, the laser holographic recording glass comprises the following components in parts by weight: SiO 2261.6 parts of Na215 portions of O, 4 portions of ZnO and Al2O38 portions of NaF 4.5 portions, KBr 3.5 portions, B2O33.2 parts of Ag20.07 part of O, Sb2O30.1 part of CeO20.03 part. The process and performance advantages of laser holographic recording glass employing this more preferred formulation are optimized.
The embodiment of the invention also provides a preparation method of the laser holographic recording glass, wherein the preparation method of the laser holographic recording glass comprises the following steps:
s100, accurately weighing the raw materials according to the proportion;
s200, finely grinding the raw materials in a mortar to enable the raw materials to be fully and uniformly mixed, and gradually adding the raw materials into a quartz crucible at 1220-1240 ℃ to enable the mixture to be melted into a glass state to obtain glass state clinker;
s300, pouring the glassy clinker into a platinum crucible in batches at 1350-1360 ℃, stirring to clarify and homogenize the glass to obtain a high-temperature melt, wherein the melting temperature is 1380-1420 ℃, and the melting time is 5-12 h;
s400, transferring the high-temperature melt into a copper mold at the temperature of 1290-1310 ℃, transferring the high-temperature melt into an annealing furnace, preserving heat at the temperature of 450-470 ℃ for 2-6 hours, and finally cooling to room temperature at a constant speed to obtain the laser holographic recording glass.
The steps S200 and S300 are processes of performing a secondary material melting process, so as to avoid damage to the platinum crucible caused by raw materials subjected to initial decomposition and melting reaction, thereby causing pollution of platinum metal particles to the holographic recording glass; in addition, in order to avoid the damage to the platinum crucible caused by the deposition of the reduced silver atoms on the bottom of the crucible during the initial chemical reaction, the preparation of the holographic recording glass is carried out by adopting a secondary material melting mode.
The step S200 is a first material melting, and in the specific implementation, the raw materials are finely ground in a mortar to be fully and uniformly mixed, and the raw materials are sequentially added into a quartz crucible heated by a silicon-carbon rod at 1220-1240 ℃ to be melted into a glass state; the step S300 is a second melting, and in the specific implementation, the glassy state holographic recording glass clinker is poured into a platinum crucible with a certain specification in batches at 1350-1360 ℃, and platinum blade slurry is adopted for stirring according to a specific process to clarify and homogenize the glass, wherein the melting temperature is 1380-1420 ℃, and the melting time is 5-12 h.
When the step S400 is specifically implemented, the high-temperature melt can be cast (or slip-cast) at 1290-1310 ℃ into a copper mold (94 aluminum bronze) at 340-360 ℃, then the copper mold is transferred into an annealing furnace, the temperature is kept at 450-470 ℃ for 2-6 h, finally the copper mold is cooled to room temperature at a cooling rate of 4-6 ℃/h, and the laser holographic recording glass is obtained by optical cold processing technologies such as cutting, rough grinding, fine grinding and polishing according to the required size specification, and can be used for the subsequent manufacturing of diffraction devices or the recording of holographic patterns.
The invention also provides a diffractive optical element or a holographic pattern product, which is made of the laser holographic recording glass. Wherein the diffractive optical element may be a transmissive and reflective volume bragg grating, a chirped volume bragg grating, or the like.
Further, an embodiment of the present invention also provides a method for manufacturing a diffractive optical device or a holographic pattern product as described above, wherein the method for manufacturing the diffractive optical device or the holographic pattern product includes the steps of:
s500, exposing the laser holographic recording glass subjected to optical cold machining, and writing interference fringes according to the designed grating period distribution; for the uniform period volume Bragg grating, exposing in a mode of double plane wave beam interference; and for the chirped volume Bragg grating, the exposure is carried out in a mode of interference of plane waves and spherical waves. The exposure writing can also be carried out by adopting a femtosecond laser direct writing mode.
S600, carrying out heat treatment on the exposed laser holographic recording glass to generate permanent refractive index change, and obtaining the diffraction optical device or the holographic pattern product, wherein the heat treatment process comprises nucleation and crystallization, and the nucleation temperature is 430-530 ℃ and the crystallization temperature is 510-540 ℃.
In specific implementation, bubble-free and streak-free glass is selected for exposure and heat treatment according to device design requirements. In the step S500, the laser hologram recording glass may be exposed by using a near ultraviolet interference exposure or a femtosecond laser direct writing method. The exposure of the diffraction device based on the holographic recording glass adopts a dual-beam interference method with a partial amplitude or a partial wave surface, and different periods are designed according to the requirements of the device. The light source can be a 325nm He-Cd laser, light beams are split after filtering, beam expanding and collimation, the light beams are reflected by a plane mirror and then are incident on the holographic recording glass sample at a proper angle, interference fringes with different spatial frequencies can be obtained by adjusting the incident angle, the interference fringes are directly exposed on the holographic recording glass sample, and the exposure dose is 0.1-3J/cm2For example, it can be selected to be 0.1J/cm2、0.3J/cm2、0.6J/cm2、0.8J/cm2、1J/cm2、1.5J/cm2、2J/cm2、3J/cm2And the like. The desired diffractive optical element, e.g. VBG, can then be obtained by thermal treatment. The exposure can also be carried out by direct writing with a femtosecond laser with 800nm wavelength or 1030nm wavelength.
The invention uses Ag+And Ce3+As the photosensitizer, AgX (X ═ Cl, Br) was used as a crystal nucleus agent, and NaF was used as a crystallization phase. The principle of the fabrication of the diffractive optical device is as follows:
the first stage, the exposure stage. Part of Ag of glass sample is irradiated by near ultraviolet light or femtosecond laser+Ions and Ce3 +The ions may release an electron.
And (3) a photosensitive process:
the second stage, crystallization nucleation stage. At a certain temperature (430-530 ℃), the released electrons are captured by another part of silver ions in the glass, and the silver ions are changed into Ag0An atom; at the same time, Br-Ion (or Cl)-Ion) and Ce4+Ion interaction to produce Br0An atom. Then Ag0Atom and Br0The atoms undergo a redox chemical reaction to produce AgBr (or AgCl). AgBr (or AgCl) is treated by heat at the nucleation temperature to diffuse and accumulate to form micro colloid (AgBr)m(or AgCl) particles, (AgBr)mMicelles give a light absorption dispersion peak around a wavelength of 450 nm. These colloids (AgBr)mThe (or AgCl) particles can serve as nuclei for nucleation of the NaF primary phase. Colloid (AgBr)mThe number and density of (or AgCl) particles is controlled by the pre-exposure dose, the higher the exposure dose, the colloid (AgBr)mThe smaller the size of the (or AgCl) particles, the greater the number.
Thermal sensitive nucleation:
the third stage, heating to 510-540 deg.C, and crystallizing with NaF (AgBr)mAnd the crystal is precipitated and grown for the center, thereby realizing the modulation of the refractive index.
Crystal growth:
the invention discloses a novel laser holographic recording glass principle, which can be used for laser holographic recording and invents a formula. The holographic recording glass is a glass which can be micro-crystallized under light induction, and an optical element manufactured by the glass inherits the excellent thermal property and mechanical property of microcrystalline glass, and simultaneously has the corrosion resistance of acid resistance and alkali resistance and the characteristic of high-power laser damage resistance of common inorganic photosensitive glass; the volume holographic grating manufactured by the method also has the characteristics of high spatial resolution and high diffraction efficiency, and has important application prospects in the fields of photoelectric detection, spectrum discrimination, spatial spectrum detection, holographic recording and the like; the diffractive optical element prepared by the glass has the characteristic of high damage threshold value, and has very important strategic significance in the fields of spectral filtering, strong laser beam synthesis, military strong laser beam control and the like.
The invention is illustrated in detail below with specific examples:
example 1
A volume Bragg grating based on laser holographic recording glass is prepared by the following steps:
first, preparing SiO as the component255 parts of Na2O12 parts, ZnO 3 parts, Al2O35 parts of NaF 4 parts of KBr 0.2 parts of B2O32 parts of Ag20.01 part of O, CeO20.01 portion of laser holographic recording glass is weighed and proportioned according to 1.4Kg, Na2O is introduced in the form of sodium nitrate, B2O3Introduced in the form of boric acid, Ag2O is introduced in the form of silver nitrate. The melting process adopts a secondary melting mode, wherein the primary melting mode uses a quartz ceramic crucible with the volume of 1L, raw materials are sequentially added into the quartz crucible heated by a silicon carbide rod at 1230 ℃, the mixture is melted into a glass state, the secondary melting mode pours glass clinker with the holographic record of the glass state into a pure platinum crucible with the caliber of phi 100mm multiplied by 100mm in batches at 1350 ℃, platinum leaf pulp is adopted to stir according to a specific process to clarify and homogenize the glass, the melting temperature is 1400 ℃, the melting time is 8h, the tapping temperature is 1300 ℃, a high-temperature melt is cast into a 94 aluminum bronze mold with the temperature of 350 ℃ at 1300 ℃, then the high-temperature melt is transferred into an annealing furnace to be annealed for 4h at 460 ℃, and finally the high-temperature melt is cooled to room temperature at the cooling speed of 5 ℃/h.
Secondly, a single collimation and filtering amplitude division grating writing system with high stability is built, and interference fringes are written into the holographic recording glass subjected to optical cold processing polishing treatment according to the designed grating period by means of a 325nm He-Cd laser at different ultraviolet exposure doses; and thirdly, generating permanent refractive index change through heat treatment, wherein the nucleation temperature is 510 ℃, and the crystallization temperature is 535 ℃, so that the required volume Bragg grating can be prepared.
Example 2
A volume Bragg grating based on laser holographic recording glass is prepared by the following steps:
first, preparing SiO as the component265 parts of Na220 portions of O, 4 portions of ZnO and Al2O39 parts of NaF 8 parts, KBr 3 parts, AgBr 1 part, KCl 1 part, BaO 2 part, B2O32 parts of La2O32 parts of Ag2O1 part, Sb2O30.3 part of SnO20.2 part of CeO21 part of laser holographic recording glass is weighed and proportioned according to 1.4Kg, Na2O is introduced in the form of sodium nitrate, B2O3Introduced in the form of boric acid, Ag2O is introduced in the form of silver nitrate. The melting process adopts a mode of secondary melting, wherein the primary melting uses a quartz ceramic crucible with the volume of 1L, raw materials are sequentially added into the quartz crucible heated by a silicon carbide rod at 1230 ℃, the mixture is melted into a glass state, the secondary melting pours glass clinker with holographic record of the glass state into a pure platinum crucible with the caliber of phi 100mm multiplied by 100mm in batches at 1360 ℃, platinum leaf pulp is adopted to stir according to a specific process for clarification and homogenization of glass, the melting temperature is 1420 ℃, the melting time is 8h, the tapping temperature is 1300 ℃, a high-temperature melt is cast into a 94 aluminum bronze mold with the temperature of 350 ℃ at 1300 ℃, then the high-temperature melt is transferred into an annealing furnace, annealed for 4h at 460 ℃, and finally cooled to room temperature at the cooling speed of 5 ℃/h.
Secondly, a single collimation and filtering amplitude division grating writing system with high stability is built, and interference fringes are written into the holographic recording glass according to the designed grating period with different ultraviolet exposure doses by means of a 325nm He-Cd laser; and thirdly, generating permanent refractive index change through heat treatment, wherein the nucleation temperature is 510 ℃, and the crystallization temperature is 535 ℃, so that the required volume Bragg grating can be prepared.
Example 3
A volume Bragg grating based on laser holographic recording glass is prepared by the following steps:
first, preparing SiO as the component260 portions of Na215 portions of O, 3 portions of ZnO and Al2O36 parts of NaF 4 parts, KBr 3 parts and La2O32 parts of Ag20.1 part of O, Sb2O30.1 part of CeO20.03 portion of laser holographic recording glass is weighed and proportioned according to 1.4Kg, Na2O is introduced in the form of sodium nitrate, B2O3Introduced in the form of boric acid, Ag2O is introduced in the form of silver nitrate. The melting process adopts a secondary melting mode, wherein the primary melting mode uses a quartz ceramic crucible with the volume of 1L, raw materials are sequentially added into the quartz crucible heated by a silicon carbide rod at 1220 ℃, so that the mixture is melted into a glass state, the secondary melting mode pours glass state holographic recording glass clinker into a pure platinum crucible with the caliber of phi 100mm multiplied by 100mm in batches at 1350 ℃, platinum leaf pulp is adopted to stir according to a specific process for clarification and homogenization of glass, the melting temperature is 1400 ℃, the melting time is 12h, the tapping temperature is 1290 ℃, a high-temperature melt is poured into a 94 aluminum bronze mold with the temperature of 340 ℃ at 1290 ℃, then the mold is transferred into an annealing furnace, the annealing is carried out for 3h at 450 ℃, and finally the mold is cooled to the room temperature at the cooling speed of 4 ℃/h.
Secondly, a single collimation and filtering amplitude division grating writing system with high stability is built, and interference fringes are written into the holographic recording glass according to the designed grating period with different ultraviolet exposure doses by means of a 325nm He-Cd laser; and thirdly, generating permanent refractive index change through heat treatment, wherein the nucleation temperature is 430 ℃, and the crystallization temperature is 510 ℃, so that the required volume Bragg grating can be prepared.
Example 4
A volume Bragg grating based on laser holographic recording glass is prepared by the following steps:
first, preparing SiO as the component262 parts of Na218 portions of O, 5 portions of ZnO and Al2O39 parts of NaF 6 parts, 5 parts of KBr, 5 parts of BaO and Ag20.2 part of O, Sb2O30.3 part of CeO20.05 portion of laser holographic recording glass is weighed and proportioned according to 1.4Kg, Na2O with nitreIntroduction of sodium in the form of B2O3Introduced in the form of boric acid, Ag2O is introduced in the form of silver nitrate. The melting process adopts a secondary melting mode, wherein the primary melting mode uses a quartz ceramic crucible with the volume of 1L, raw materials are sequentially added into the quartz crucible heated by a silicon carbide rod at 1240 ℃ to melt the mixture into a glass state, the secondary melting mode pours glass state holographic recording glass clinker into a pure platinum crucible with the caliber of phi 100mm multiplied by 100mm in batches at 1360 ℃, platinum leaf pulp is adopted to stir according to a specific process to clarify and homogenize the glass, the melting temperature is 1420 ℃, the melting time is 5h, the tapping temperature is 1310 ℃, high-temperature melt is cast into a 94 aluminum bronze mold with the temperature of 360 ℃ at 1310 ℃, then the mold is transferred into an annealing furnace to be annealed for 6h at 470 ℃, and finally the temperature is cooled to the room temperature at the cooling speed of 6 ℃/h.
Secondly, a single-collimation and filtering amplitude-division grating writing system with high stability is built, and interference fringes are written into the holographic recording glass by different ultraviolet exposure doses according to a designed grating period with the help of a 325nm He-Cd laser; and thirdly, generating permanent refractive index change through heat treatment, wherein the nucleation temperature is 530 ℃, and the crystallization temperature is 540 ℃, so that the required volume Bragg grating can be prepared.
Example 5
A volume Bragg grating based on laser holographic recording glass is prepared by the following steps:
first, preparing SiO as the component261.6 parts of Na215 portions of O, 4 portions of ZnO and Al2O38 portions of NaF 4.5 portions, KBr 3.5 portions, B2O33.2 parts of Ag20.07 part of O, Sb2O30.1 part of CeO20.03 portion of laser holographic recording glass is weighed and proportioned according to 1.4Kg, Na2O is introduced in the form of sodium nitrate, B2O3Introduced in the form of boric acid, Ag2O is introduced in the form of silver nitrate. The melting process adopts a mode of secondary melting, the primary melting uses a quartz ceramic crucible with the volume of 1L, raw materials are added into the quartz crucible heated by a silicon carbide rod in sequence at 1230 ℃, the mixture is melted into glass state, and the secondary melting is carried outPouring glassy state holographic recording glass clinker into a pure platinum crucible with the caliber of phi 100mm multiplied by 100mm in batches at 1350 ℃, stirring by adopting platinum blade slurry according to a specific process to clarify and homogenize the glass, wherein the melting temperature is 1420 ℃, the melting time is 6h, the tapping temperature is 1300 ℃, casting a high-temperature melt into a 94 aluminum bronze mold with the temperature of 350 ℃ at 1300 ℃, then transferring into an annealing furnace, annealing for 2h at 460 ℃, and finally cooling to the room temperature at the cooling speed of 5 ℃/h.
Secondly, a single collimation and filtering amplitude division grating writing system with high stability is built, and interference fringes are written into the holographic recording glass according to the designed grating period with different ultraviolet exposure doses by means of a 325nm He-Cd laser; and thirdly, generating permanent refractive index change through heat treatment, wherein the nucleation temperature is 510 ℃, and the crystallization temperature is 535 ℃, so that the required volume Bragg grating can be prepared.
Example 6
A holographic pattern product based on laser holographic recording glass is prepared by the following steps:
first, preparing SiO as the component261.6 parts of Na215 portions of O, 4 portions of ZnO and Al2O38 portions of NaF 4.5 portions, KBr 3.5 portions, B2O33.2 parts of Ag20.07 part of O, Sb2O30.1 part of CeO20.03 portion of laser holographic recording glass is weighed and proportioned according to 1.4Kg, Na2O is introduced in the form of sodium nitrate, B2O3Introduced in the form of boric acid, Ag2O is introduced in the form of silver nitrate. The melting process adopts a mode of secondary melting, wherein the primary melting uses a quartz ceramic crucible with the volume of 1L, raw materials are sequentially added into the quartz crucible heated by a silicon carbide rod at 1230 ℃, the mixture is melted into a glass state, the secondary melting pours glass clinker for holographic record of the glass state into a pure platinum crucible with the caliber of phi 100mm multiplied by 100mm in batches at 1350 ℃, platinum leaf pulp is adopted to stir according to a specific process for clarification and homogenization of glass, the melting temperature is 1420 ℃, the melting time is 6h, the tapping temperature is 1300 ℃, a high-temperature melt is cast into a 94 aluminum bronze mold with the temperature of 350 ℃ at 1300 ℃, and then the mold is transferred into a retreating modeAnnealing at 460 ℃ for 2h in a fire furnace, and finally cooling to room temperature at a cooling rate of 5 ℃/h.
Secondly, a single-collimation and filtering amplitude-division double-beam laser interference pattern writing system with high stability is built according to the required holographic pattern, and interference fringe patterns are written into the holographic recording glass with a certain ultraviolet exposure dose by means of a 250-350nm wave band ultraviolet laser (such as a 325nm He-Cd laser); and thirdly, generating permanent refractive index change through heat treatment, wherein the nucleation temperature is 510 ℃, and the crystallization temperature is 535 ℃, so that the required holographic pattern product can be prepared.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (7)
1. The laser holographic recording glass is characterized by comprising the following components in parts by weight:
wherein, by KBr and Ag2And introducing Ag ions and Br ions into the O to form an AgBr crystal nucleating agent.
2. The laser holographic recording glass according to claim 1, comprising the components in parts by weight:
3. the method for producing a laser hologram recording glass according to any one of claims 1 to 2, wherein the method for producing a laser hologram recording glass comprises the steps of:
accurately weighing the raw materials according to the proportion;
finely grinding the raw materials in a mortar to enable the raw materials to be fully and uniformly mixed, and gradually adding the raw materials into a quartz crucible at 1220-1240 ℃ to enable the mixture to be melted into a glass state to obtain glass state clinker;
pouring the glassy clinker into a platinum crucible in batches at 1350-1360 ℃, stirring to clarify and homogenize glass to obtain a high-temperature melt, wherein the melting temperature is 1380-1420 ℃, and the melting time is 5-12 h;
transferring the high-temperature melt into a copper mold at the temperature of 1290-1310 ℃, transferring the high-temperature melt into an annealing furnace, preserving the heat at the temperature of 450-470 ℃ for 2-6 hours, and finally cooling to room temperature at a constant speed to obtain the laser holographic recording glass.
4. The preparation method of the laser holographic recording glass according to claim 3, wherein the laser holographic recording glass is obtained by cooling to room temperature at a cooling rate of 4-6 ℃/h.
5. A diffractive optical element or a hologram pattern article, which is produced by using the laser hologram recording glass according to any one of claims 1 to 2.
6. A method of making a diffractive optical element or a holographic patterned article according to claim 5, comprising the steps of:
exposing the laser holographic recording glass, and writing interference fringes according to a designed grating period;
and carrying out heat treatment on the exposed laser holographic recording glass to generate permanent refractive index change so as to obtain the diffraction optical device or the holographic pattern product, wherein the heat treatment process comprises nucleation and crystallization, the nucleation temperature is 430-530 ℃, and the crystallization temperature is 510-540 ℃.
7. The method of claim 6, wherein the laser holographic recording glass is exposed by near-UV interference exposure or femtosecond laser direct writing.
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| CN115432922B (en) * | 2022-08-31 | 2023-09-19 | 成都光明光电有限责任公司 | Photo-thermal refraction glass and preparation method thereof |
| CN115403267B (en) * | 2022-08-31 | 2023-08-22 | 成都光明光电有限责任公司 | Photo-thermal refraction glass and preparation method thereof |
| CN115572063B (en) * | 2022-08-31 | 2023-10-03 | 成都光明光电有限责任公司 | Photothermographic variable glass with low melting temperature and preparation method thereof |
| CN115572065B (en) * | 2022-08-31 | 2024-04-02 | 成都光明光电有限责任公司 | Photothermal sensitive refractive glass with low absorption loss and preparation method thereof |
| CN115417597B (en) * | 2022-08-31 | 2023-08-18 | 成都光明光电有限责任公司 | Photothermographic variable glass with high transition temperature and preparation method thereof |
| CN115677210B (en) * | 2022-09-04 | 2023-11-14 | 苏州东辉光学有限公司 | Volume scattering light homogenizing sheet and preparation method thereof |
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