CN108821569A - Laser holographic recording glass, diffraction optical device or hologram pattern product and preparation method - Google Patents
Laser holographic recording glass, diffraction optical device or hologram pattern product and preparation method Download PDFInfo
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- CN108821569A CN108821569A CN201810333771.0A CN201810333771A CN108821569A CN 108821569 A CN108821569 A CN 108821569A CN 201810333771 A CN201810333771 A CN 201810333771A CN 108821569 A CN108821569 A CN 108821569A
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- 239000011521 glass Substances 0.000 title claims abstract description 179
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 230000003287 optical effect Effects 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 26
- 230000008018 melting Effects 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000005352 clarification Methods 0.000 claims abstract description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 17
- 238000010899 nucleation Methods 0.000 claims description 16
- 230000006911 nucleation Effects 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 41
- 239000000377 silicon dioxide Substances 0.000 abstract description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052593 corundum Inorganic materials 0.000 abstract description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 17
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 abstract description 16
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 15
- 229910052681 coesite Inorganic materials 0.000 abstract description 15
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 15
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 abstract description 15
- 229910052682 stishovite Inorganic materials 0.000 abstract description 15
- 229910052905 tridymite Inorganic materials 0.000 abstract description 15
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000265 homogenisation Methods 0.000 abstract description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 abstract description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052709 silver Inorganic materials 0.000 abstract description 8
- 239000004332 silver Substances 0.000 abstract description 8
- 230000006378 damage Effects 0.000 abstract description 7
- 239000002667 nucleating agent Substances 0.000 abstract description 7
- -1 silver halide Chemical class 0.000 abstract description 7
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011780 sodium chloride Substances 0.000 abstract description 5
- 230000009477 glass transition Effects 0.000 abstract description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 239000011734 sodium Substances 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 13
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 10
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229910021607 Silver chloride Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 238000013021 overheating Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 229910001961 silver nitrate Inorganic materials 0.000 description 6
- 239000004317 sodium nitrate Substances 0.000 description 6
- 235000010344 sodium nitrate Nutrition 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 238000010309 melting process Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010079 rubber tapping Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 3
- 239000006132 parent glass Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 208000033999 Device damage Diseases 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 229910006295 Si—Mo Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000008832 photodamage Effects 0.000 description 1
- 239000006089 photosensitive glass Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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
-
- 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
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
-
- 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
- G02B5/1847—Manufacturing methods
- G02B5/1857—Manufacturing methods using exposure or etching means, e.g. holography, photolithography, exposure to electron or ion beams
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses laser holographic recording glass, diffraction optical device or hologram pattern product and preparation method, the laser holographic recording glass, by weight, including component：SiO255~65 parts, Na212~20 parts of O, (ZnO+Al2O3) 8~13 parts, 4~8 parts of NaF, 0.2~5 part of (KBr+AgBr+NaBr+NaCl+KCl), (BaO+La2O3+B2O3) 2~6 parts, Ag20.01~1 part of O, (Sb2O3+SnO2) 0~1 part, CeO20.01~1 part.Laser holographic recording glass melting temperature of the present invention is low, 1380~1420 DEG C can clarification and homogenization, and heat treatment temperature be lower than glass transition temperature, substantially increase device yield；Using silver halide as Nucleating Agent, damage threshold also significantly improves laser holographic recording glass of the present invention simultaneously.
Description
Technical field
The present invention relates to glass technology field more particularly to a kind of laser holographic recording glass, diffraction optical device or complete
Cease pattern article and preparation method.
Background technique
Laser holographic recording glass is that there is one kind photo-thermal to sell off (Photo-Thermo-Refractive, abbreviation PTR) effect
The glass answered contains the photosensitive factor (Ce in the glass3+、Ag+), glass can generate phase transformation after uv-exposure and heat treatment,
So that the refractive index of exposure region glass changes, there are tens to several hundred ppm refringence (Δ n), benefits with unexposed area
With this characteristic using interference exposure by the way of may be implemented phase-type volume Bragg grating (Volume Bragg Grating,
Abbreviation VBG), laser hologram aim at record and the preparation of the diffraction optical elements such as mirror, this kind of glass has that thermal stability is good, damage
The advantages that threshold value is high, light sensitivity is good.
VBG diffraction optical element based on laser holographic recording glass, it is close in compression and broadening, the angle selection of laser pulse
Field filtering, semiconductor laser output spectrum is stable, laser output mode selects and the advanced laser technology aspects such as holographic recording
There is important application prospect.
The VBG of high-diffraction efficiency can greatly improve the performance of laser and its system, and how research improves body grating
Diffraction efficiency, preparing efficient VBG has great significance.Refractive index modulation of the diffraction efficiency of VBG by grating
(Δ n), grating thickness (d), laser holographic recording glass are to the absorption characteristic (α) of exposure wavelength, laser holographic recording glass for degree
The parameters such as uniformity influence, and these parameters are related with the characteristic of laser holographic recording glass itself.
In the world, Glebov of Florida, US National Central University et al. is by optimization PTR glass formula, the property prepared
The excellent PTR glass of energy, and it is used successfully to the preparation of VBG, the VBG bore that can be prepared at present is up to 100mm.
The country, University Of Suzhou are ground from the preparation characteristic of PTR glass ingredient, heat treatment process etc. to body grating
Study carefully, took the lead in developing PTR glass in 2012, and be used for the production of high efficiency body grating；2013, Beijing University of Technology was to body
The change wavelength of grating reads characteristic, and laser irradiation stability is studied；2015, China Building Material Scientific Research General Institute
It is prepared for PTR glass, obtains the affecting laws of uv-exposure dosage refractive index modulation degree.
2003, the PTR glass composition of U.S. Efimov et al. invention was as follows：13.6Na2O-5.2ZnO-2.3Al2O3-
72.3SiO2-3.7NaF-1.5KBr-1.2AlF3(mol%), while doped with 0.01Ag2O-0.01CeO2-0.001SnO2-
0.03Sb2O3(mol%) (United States Patent (USP) US6,586,141B1).The glass is a kind of devitrified glass, using silver as Nucleating Agent, is led to
The mode for crossing uv-exposure realizes Controlled Crystallization, and holographic recording principle is as follows：The quick first stage glass sample of photo-thermal is near ultraviolet
Under the irradiation of light, Ce3+It is oxidized to Ce4+An electronics is released, the electronics of release is captured by silver ion, and silver ion becomes Ag0；
In nucleation temperature (450~500 DEG C), nearby quickly diffusion, accumulation form small silver-colored crystal to second stage silver atoms, then produce
Raw a large amount of galactic nucleus；Phase III is warming up in 500~550 DEG C of temperature ranges, under the induction of these galactic nucleus particles, in glass
F-Ion and Na+Ion is assembled to form NaF crystal to galactic nucleus, and nucleus number is most in exposure area, in crystallization post-exposure region
NaF crystal volume fraction highest, therefore variations in refractive index is about big.The refractive index of NaF crystal is 1.32, and unexposed area glass
Refractive index be 1.49, by spectrum assignment formed variations in refractive index can realize holographic recording.
The laser holographic recording glass smelting temperature of U.S. Efimov et al. invention is high, 1450~1500 DEG C, need using
Si-Mo rod melting stove heating, glass melting are at high cost；Meanwhile heat-treatment temperature range is at 480~580 DEG C, it is soft more than glass
Change temperature spot, glass is easy to happen deformation when preparing device, is difficult to control, causes device yield low.Traditional holographic recording
Glass PTR glass is collected as nano-Ag particles as Nucleating Agent using silver, and after being prepared into holographic optical elements (HOE), Argent grain is present in glass
In glass element, cause prepared device damage threshold value low.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of laser holographic recording glass, diffraction
Optical device or hologram pattern product and preparation method, it is intended to solve existing laser holographic recording glass smelting temperature height, lead
Cause melting it is at high cost, heat treatment temperature be more than glass transition temperature point, when preparing device glass easily deformation occurs, cause device at
The low problem of the device damage threshold value of the low and traditional holographic recording glass preparation of product rate.
Technical scheme is as follows：
The present invention provides a kind of laser holographic recording glass, by weight, including component：SiO255~65 parts, Na2O
12~20 parts, (ZnO+Al2O3) 8~13 parts, 4~8 parts of NaF, 0.2~5 part of (KBr+AgBr+NaBr+NaCl+KCl), (BaO+
La2O3+B2O3) 2~6 parts, Ag2O0.01~1 part, (Sb2O3+SnO2) 0~1 part, CeO20.01~1 part.
Preferably, the laser holographic recording glass, wherein by weight, including component：SiO260~62 parts,
Na215~18 parts of O, 3~5 parts of ZnO, Al2O35~9 parts, 4~6 parts of NaF, 3~5 parts of KBr, B2O32~5 parts, Ag2O
0.05~0.07 part, Sb2O30.1~0.3 part, CeO20.03~0.05 part.
It is furthermore preferred that the laser holographic recording glass, wherein by weight, including component：SiO261.6 part,
Na215 parts of O, 4 parts of ZnO, Al2O38 parts, 4.5 parts of NaF, 3.5 parts of KBr, B2O33.2 parts, Ag20.07 part of O, Sb2O3 0.1
Part, CeO20.03 part.
The preparation method for the laser holographic recording glass that the present invention also provides a kind of as described in any of the above item, wherein institute
The preparation method for stating laser holographic recording glass includes step：
Accurate weighing raw material according to the ratio；
The fine grinding in mortar by raw material, makes its full and uniform mixing, and raw material is gradually added at 1220~1240 DEG C
Into silica crucible, mixture is made to be fused into glassy state, obtains glassy state clinker；
Glassy state clinker is poured into platinum crucible in batches at 1350~1360 DEG C, stirring with carry out glass clarification and
Homogenizing, obtains high-temperature fusant, and during which glass melting temperature is 1380~1420 DEG C, and melting time is 5~12h；
High-temperature fusant is transferred in 340~360 DEG C of copper mould at 1290~1310 DEG C, after be transferred in annealing furnace,
2~6h is kept the temperature at 450~470 DEG C, is finally at the uniform velocity cooled to room temperature, is obtained laser holographic recording glass.
The preparation method of the laser holographic recording glass, wherein room temperature is cooled to the cooling rate of 4~6 DEG C/h,
Laser holographic recording glass is obtained by the optics cold machining process such as cutting, corase grinding, fine grinding and polishing by required dimensions,
It can be used for the record of subsequent diffractive optical element production or hologram pattern.
The present invention also provides a kind of diffraction optical device or hologram pattern products, wherein using described in any of the above item
Laser holographic recording glass is made.
The present invention also provides the preparation method of a kind of diffraction optical device as described above or hologram pattern product,
In, the preparation method of the diffraction optical device or hologram pattern product includes step：
Laser holographic recording glass is exposed, interference fringe is written by designed screen periods；
Laser holographic recording glass after exposure is heat-treated, permanent refractive index variation is generated, obtains diffraction light
Learn device or hologram pattern product, wherein heat treatment process includes nucleation and crystallization, and nucleation temperature is 430~530 DEG C, crystallization
Temperature is 510~540 DEG C.
The preparation method of the diffraction optical device or hologram pattern product, wherein exposed using the interference of near ultraviolet light source
The mode of light or femtosecond laser light source direct write is exposed laser holographic recording glass；For uniform period body Prague light
Grid are exposed by the way of biplane glistening light of waves beam interferometer；For chirp volume Bragg grating, using plane wave and spherical surface wave interference
Mode expose.
Beneficial effect：The present invention provides a kind of laser holographic recording glass, diffraction optical device or hologram pattern products
And preparation method, laser holographic recording glass melting temperature of the present invention is low, 1380~1420 DEG C can clarification and homogenization, make
Can be completed with common Elema electric furnace it is melted, and heat treatment temperature be lower than glass transition temperature, substantially increase device
Yield rate；Meanwhile laser holographic recording glass of the present invention, using silver halide as Nucleating Agent, the later period can by secondary lighting process
So that silver halide decomposes, silver-colored particle size is significantly smaller than conventional PTR glass in resulting product, therefore damage threshold can be shown
It writes and improves.
Specific embodiment
The present invention provides a kind of laser holographic recording glass, diffraction optical device or hologram pattern product and preparation method,
To make the purpose of the present invention, technical solution and effect clearer, clear and definite, the present invention is described in more detail below.It should
Understand, the specific embodiments described herein are merely illustrative of the present invention, is not intended to limit the present invention.
A kind of laser holographic recording glass that present pre-ferred embodiments provide, by weight, including component：SiO2
55~65 parts, Na212~20 parts of O, (ZnO+Al2O3) 8~13 parts, 4~8 parts of NaF, (KBr+AgBr+NaBr+NaCl+KCl)
0.2~5 part, (BaO+La2O3+B2O3) 2~6 parts, Ag2O0.01~1 part, (Sb2O3+SnO2) 0~1 part, CeO20.01~1 part.
Further, SiO2It is the host oxide of parent glass, with oxygen-octahedron [SiO2] structural unit mutually interconnect
It connects to form irregular contiguous network body, which is the skeleton of parent glass.SiO2The increase of content is conducive to glass machine
The improvement of tool intensity, however when too high levels glass can become be difficult to melt.In the present embodiment, SiO2Content be 55~65
Part, such as can be 55 parts, 58 parts, 60 parts, 62 parts, 65 parts etc..
Further, Na2O plays the role of cosolvent and clarifying agent, with NaNO3Or Na2CO3Form introduce.Na2O is
The network modifying oxide of parent glass network body, it can provide sodium ion Na+It occupy in the hole of network body, in addition to this
Free oxygen, which can be provided, makes [SiO2] the O/Si ratio in network body increases, silicon oxygen bond is broken, so that the viscosity of glass is reduced,
Make glass be easy to melt, is also beneficial to the clarification of glass.But Na2The introduction volume of O cannot be excessive, otherwise will lead to the heat of glass
The coefficient of expansion increases, and thermal stability, chemical stability and the mechanical strength of glass reduce.In the present embodiment, Na2The content of O
It is 12~20 parts, such as can is 12 parts, 15 parts, 17 parts, 18 parts, 20 parts etc..
Further, ZnO and Al2O3Be introduced for reduce glass tendency towards devitrification, improve the chemical stabilization of glass
Property, thermal stability and mechanical strength, reduce the thermal expansion coefficient of glass.ZnO is intermediate oxide, under normal circumstances, with
Zinc oxygen octahedra [ZnO6] be used as network body external oxidation object that can form zinc oxygen tetrahedron when the free oxygen in glass is enough
[ZnO4] and into the structural network of glass, keep the structure of glass more stable.Al2O3It is also intermediate oxide, in glass
There are two types of co-ordination states, i.e. [AlO4] and [AlO6].When free oxygen is more with [AlO4] state presence, then when free hypoxgia
With [AlO6] exist.When it is located at high co-ordination state, glass refractive index with higher and lesser molecular volume；At it
When low co-ordination state, the refractive index and density of glass are reduced.In the present embodiment, ZnO+Al2O3Content be 8~13 parts, example
It such as can be 8 parts, 10 parts, 12 parts, 13 parts.
Further, NaF is the light-operated crystallization component of glass.NaF content cannot be too low, and too low meeting is so that after exposure heat treatment
The refractive index modulation degree of acquisition is too low；NaF content can not be too high, otherwise glass can be made to be easy for crystallization in preparatory phase.?
In the present embodiment, the content of NaF is 4~8 parts, such as can be 4 parts, 5 parts, 6 parts, 7 parts, 8 parts etc..
Further, the formation of Nucleating Agent AgBr/AgCl is with AgNO3Or the form of AgCl+ halide introduces.Wherein,
Ag2O is with during photothermal treatment, Ag2The silver ion part that O is provided is reduced to silver atoms, and halide ion is oxidized to halogen
Atom, during heat treatment, chemical reaction occurs the glass after illumination at a certain temperature for silver atoms and halogen atom together
Generate silver halide micelle.In the present embodiment, the content of (KBr+AgBr+NaBr+NaCl+KCl) is 0.2~5 part, Ag2O's contains
Amount is 0.01~1 part.For example, (KBr+AgBr+NaBr+NaCl+KCl) can be 0.2 part, 0.8 part, 1 part, 3 parts, 5 parts etc.,
Ag2O can be 0.01 part, 0.1 part, 0.5 part, 1 part etc..
Further, the introducing of barium monoxide and lanthana.BaO is also network modifying oxide, it can increase glass
Refractive index, density, gloss and chemical stability.A small amount of BaO can accelerate the fusing of glass, glass can be made to exist when too high levels
It is clarified in melting process difficult.Suitable BaO is added in glass can improve the ability for absorbing exposure.La2O3Glass can be improved
Chemical stability.B2O3SiO can partially be substituted by generating body as glass2, in the case where not influencing glass overall performance, drop
The glass melting temperature of low glass.In the present embodiment, (BaO+La2O3+B2O3) content be 2~6 parts, such as can be 2 parts, 4
Part, 5 parts, 6 parts etc..
It further,, in glass can be in order to make bubble in glass be easy to eliminate during holographic glass preparation
Introduce suitable Sb2O3Or SnO2, Sb2O3In 600~1200 DEG C of temperature-rise periods, absorb what nitrate in raw material decomposed to give off
Oxygen becomes Sb2O5, CeO at 1380~1420 DEG C of clarifying temp, in glass2、Sb2O5Or SnO2, decompose to give off oxygen confession
Bubble is eliminated in glass metal clarification, and reaction process is as follows：
In the present embodiment, (Sb2O3+SnO2) content be 0~1 part, such as can be 0 part, 0.3 part, 0.6 part, 1 part
Deng.
Further, present invention introduces a small amount of CeO2Mainly play the role of photosensitivity promotor, part cerium is provided
Ion is with three valence state Ce3+Form exist in glass, Ce3+It itself is ionized under ultraviolet irradiation condition and releases an electricity
Son, the electronics and silver ion Ag+In conjunction with the photosensitive reduction process that can promote silver ion.In the present embodiment, CeO2Content be
0.01~1 part, such as can be 0.01 part, 0.03 part, 0.05 part, 0.1 part, 1 part etc..
Laser holographic recording glass of the present invention has following technique and feature performance benefit：1), glass melting temperature is low, 1380~
1420 DEG C can clarification and homogenization, can be completed using ordinary silicon carbon bar furnace melted；2), holographic recording heat treatment temperature is lower than
Glass transition temperature substantially increases the yield rate of device；3), using silver halide as Nucleating Agent, the later period passes through secondary the present invention
Lighting process can be such that silver halide decomposes, and silver-colored particle size is significantly smaller than conventional PTR glass in resulting product, therefore damages
Threshold value can significantly improve.
Preferably, the laser holographic recording glass, wherein by weight, including component：SiO260~62 parts,
Na215~18 parts of O, 3~5 parts of ZnO, Al2O35~9 parts, 4~6 parts of NaF, 3~5 parts of KBr, B2O32~5 parts, Ag2O
0.05~0.07 part, Sb2O30.1~0.3 part, CeO20.03~0.05 part.Wherein, the content of ZnO can be 3 parts, 4 parts, 5 parts
Deng Al2O3Content can be 5 parts, 8 parts, 9 parts etc., the content of KBr can be 3 parts, 4 parts, 5 parts etc., B2O3Content can be with
It is 2 parts, 4 parts, 5 parts etc., Sb2O3Content can be 0.1 part, 0.2 part, 0.3 part etc..Using the laser hologram of this optimization formula
Recording glass has more preferably technique and feature performance benefit.
It is furthermore preferred that the laser holographic recording glass, wherein by weight, including component：SiO261.6 part,
Na215 parts of O, 4 parts of ZnO, Al2O38 parts, 4.5 parts of NaF, 3.5 parts of KBr, B2O33.2 parts, Ag20.07 part of O, Sb2O3 0.1
Part, CeO20.03 part.It is best using the technique and feature performance benefit of this laser holographic recording glass being more preferably formulated.
The embodiment of the present invention also provides a kind of preparation method of laser holographic recording glass as described above, wherein institute
The preparation method for stating laser holographic recording glass includes step：
S100, according to the ratio accurate weighing raw material；
S200, the fine grinding in mortar by raw material, make its full and uniform mixing, 1220~1240 DEG C by raw material gradually
It is added in silica crucible, mixture is made to be fused into glassy state, obtain glassy state clinker；
S300, glassy state clinker poured into platinum crucible at 1350~1360 DEG C in batches, is stirred to carry out glass
Clarification and homogenization obtain high-temperature fusant, and during which glass melting temperature is 1380~1420 DEG C, and melting time is 5~12h；
S400, high-temperature fusant is transferred in 340~360 DEG C of copper mould at 1290~1310 DEG C, after be transferred to annealing
In furnace, 2~6h is kept the temperature at 450~470 DEG C, room temperature is finally at the uniform velocity cooled to, obtains laser holographic recording glass.
The step S200 and step S300 that is to say the process for carrying out secondary material, in order to avoid occur initial decomposition,
The raw material of frit reaction generate damage to platinum crucible, the pollution so as to cause platinum particle to holographic recording glass；This
Outside, crucible bottom is deposited to also for the silver atoms for avoiding the beginning from being reduced during chemically reacting and damage is generated to platinum crucible, therefore adopt
The preparation of holographic recording glass is carried out with the mode of secondary material.
The step S200 is first time material, when it is implemented, making raw material fine grinding in mortar, keeps it sufficiently equal
Raw material is gradually added in the silica crucible by Elema heating at 1220~1240 DEG C, is fused into mixture by even mixing
Glassy state；The step S300 is second of material, when it is implemented, can be at 1350~1360 DEG C by glassy state holographic recording
Glass clinker is poured into batches in the platinum crucible of certain specification, uses the slurry stirring of platinum leaf to carry out glass according to specific technique
Clarification and homogenization, during which glass melting temperature be 1380~1420 DEG C, melting time be 5~12h.
The step S400 is when it is implemented, can arrive high-temperature fusant casting (or leakage is cast) at 1290~1310 DEG C
In 340~360 DEG C of copper mould (94 aluminium bronze), after be transferred in annealing furnace, 450~470 DEG C nearby keep the temperature 2~6h, finally
It is cooled to room temperature with the cooling rate of 4~6 DEG C/h, by required dimensions, by optics such as cutting, corase grinding, fine grinding and polishings
Cold machining process obtains laser holographic recording glass, can be used for the record of subsequent diffractive optical element production or hologram pattern.
The present invention also provides a kind of diffraction optical device or hologram pattern products, use laser described in any of the above item
Holographic recording glass is made.Wherein, the diffraction optical device can be transmission-type and reflective volume Bragg grating, chirp body
Bragg grating etc..
Further, the embodiment of the present invention also provides a kind of diffraction optical device as described above or hologram pattern product
Preparation method, wherein the preparation method of the diffraction optical device or hologram pattern product includes step：
S500, the laser holographic recording glass after optics is cold worked is exposed, by designed screen periods point
Interference fringe is written in cloth；For uniform period volume Bragg grating, exposed by the way of biplane glistening light of waves beam interferometer；For Zhou
It sings volume Bragg grating, is exposed by the way of plane wave and spherical surface wave interference.It can also be by the way of femtosecond laser direct write
It is exposed write-in.
S600, the laser holographic recording glass after exposure is heat-treated, generates permanent refractive index variation, is spread out
Penetrate optical device or hologram pattern product, wherein heat treatment process includes nucleation and crystallization, and nucleation temperature is 430~530 DEG C,
Crystallization temperature is 510~540 DEG C.
In the specific implementation, needs are designed according to device, select bubble-free, estriate glass be exposed and heat at
Reason.In the step S500, laser hologram can be remembered in such a way that black light interferes exposure or femtosecond laser direct write
Record glass is exposed.The exposure of diffractive optical element based on holographic recording glass, which uses, divides amplitude or wave-front division two-beam interference side
Method needs to design the different periods according to device.Light source may be selected 325nm He-Cd laser, light beam filtered, expand and
Beam splitting after collimation can be with by adjusting incident angle with appropriate angle incidence holographic recording glass sample after plane mirror reflects
The interference fringe of different space frequency is obtained, which is directly exposed on holographic recording glass sample, and exposure dose is
0.1~3J/cm2, such as may be selected to be 0.1J/cm2、0.3J/cm2、0.6J/cm2、0.8J/cm2、1J/cm2、1.5J/cm2、2J/
cm2、3J/cm2Etc. parameters.Then required diffraction optical element, such as VBG can be obtained by heat treatment.Exposure can also be used
The mode of the femto-second laser direct write of 800nm wavelength or 1030nm wavelength carries out.
The present invention is with Ag+And Ce3+As photosensitizer, AgX (X=Cl, Br) is used as Nucleating Agent, and NaF is as crystallization crystal phase.Spread out
The preparation principle for penetrating optical device is as follows：
First stage, exposure stage.Glass sample part Ag under the irradiation of black light or femtosecond laser+Ion and Ce3 +Ion can release an electronics.
Photosensitive process：
Second stage, crystallization nucleation stage.Under certain temperature (430~530 DEG C), the electronics of release is by another in glass
A part of silver ion capture, silver ion become Ag0Atom；Meanwhile Br-Ion (or Cl-Ion) and Ce4+Ionic interaction is raw
At Br0Atom.Then Ag0Atom and Br0Atom occurs redox chemistry reaction and generates AgBr (or AgCl).AgBr (or
AgCl) diffusion occurs for heat treatment under nucleation temperature, accumulation forms small colloid (AgBr)m(or AgCl) particle, (AgBr)m
Micelle generates the light absorption disperse peak near 450nm wavelength.These colloids (AgBr)m(or AgCl) particle can be used as nucleus and lure
Lead the nucleus of NaF primary phase generation.Colloid (AgBr)mControl of the quantity and density of (or AgCl) particle by exposure dose early period
System, exposure dose is higher, colloid (AgBr)mThe size of (or AgCl) particle is smaller, and quantity is more.
Temperature-sensitive nucleation：
Phase III is warming up in 510~540 DEG C of temperature ranges, and NaF crystal is with (AgBr)mCentered on be precipitated generate simultaneously
It grows up, to realize refractive index modulation.
Crystal growth：
It present invention finds a kind of new laser holographic recording glass principle, can be used for laser holographic recording, and invent
Formula.Holographic recording glass of the present invention be under a kind of photoinduction can controlled micro crystallization glass, inherited by the optical element of its production
The outstanding thermal characteristic of devitrified glass and mechanical property, while there is acidproof, the alkaline-resisting corrosivity of general inorganic photosensitive glass
With anti-high power laser light damage feature；The spy of high spatial resolution and high-diffraction efficiency is also equipped with by its volume holographic grating made
Property, the fields such as photodetection and spectrum examination, spatial spectral detection, holographic recording are with important application prospects；Using the glass
The diffraction optical element of glass preparation, has the characteristics that damage threshold is high, in spectral filtering, intense laser beam synthesis, military light laser
Beam Control, field have very important strategic importance.
It is elaborated below with specific embodiment to the present invention：
Embodiment 1
A kind of volume Bragg grating based on laser holographic recording glass, preparation method include step：
The first step, preparation group are divided into SiO255 parts, Na212 parts of O, 3 parts of ZnO, Al2O35 parts, 4 parts of NaF, KBr 0.2
Part, B2O32 parts, Ag20.01 part of O, CeO20.01 part of laser holographic recording glass carries out weighing proportion, Na by 1.4Kg2O
It is introduced in the form of sodium nitrate, B2O3It is introduced in the form of boric acid, Ag2O is introduced in the form of silver nitrate.Melting process uses two
Raw material, is gradually added to by silicon by the mode of secondary material, the quartz ceramic crucible that a material is 1L using volume at 1230 DEG C
In the silica crucible of carbon-point heating, mixture is set to be fused into glassy state, secondary material is at 1350 DEG C by glassy state holographic recording
Glass clinker is poured into batches in the pure platinum crucible of Φ 100mm × 100mm bore, is stirred according to specific technique using platinum leaf slurry
It mixes to carry out the clarification and homogenization of glass, glass melting temperature is 1400 DEG C, melting time 8h, 1300 DEG C of tapping temperature, 1300
High-temperature fusant is cast in 350 DEG C of 94 aluminium bronze molds at DEG C, after be transferred in annealing furnace, anneal 4h at 460 DEG C, finally
Room temperature is cooled to the cooling rate of 5 DEG C/h.
Second step, builds single collimation of high stability, filtering divides amplitude grating writing system, by means of 325nmHe-
Cd laser, with different uv-exposure dosage by designed screen periods in the holographic note by optics cold working polishing treatment
Interference fringe is written in record glass；Third step generates permanent refractive index through Overheating Treatment and changes, and 510 DEG C of nucleation temperature, crystallization
535 DEG C of temperature, required volume Bragg grating can be prepared.
Embodiment 2
A kind of volume Bragg grating based on laser holographic recording glass, preparation method include step：
The first step, preparation group are divided into SiO265 parts, Na220 parts of O, 4 parts of ZnO, Al2O39 parts, 8 parts of NaF, KBr 3
Part, 1 part of AgBr, 1 part of KCl, 2 parts of BaO, B2O32 parts, La2O32 parts, Ag21 part of O, Sb2O30.3 part, SnO20.2 part,
CeO21 part of laser holographic recording glass carries out weighing proportion, Na by 1.4Kg2O is introduced in the form of sodium nitrate, B2O3With boron
The form of acid introduces, Ag2O is introduced in the form of silver nitrate.For melting process by the way of secondary material, a material uses appearance
Product is the quartz ceramic crucible of 1L, and raw material is gradually added in the silica crucible by Elema heating at 1230 DEG C, makes to mix
Material is fused into glassy state, secondary material at 1360 DEG C by glassy state holographic recording glass clinker pour into batches Φ 100mm ×
In the pure platinum crucible of 100mm bore, uses the stirring of platinum leaf slurry to carry out the clarification and homogenization of glass according to specific technique, melt
Temperature processed is 1420 DEG C, melting time 8h, and 1300 DEG C of tapping temperature, high-temperature fusant is cast to 350 DEG C at 1300 DEG C
In 94 aluminium bronze molds, after be transferred in annealing furnace, anneal 4h at 460 DEG C, is finally cooled to room with the cooling rate of 5 DEG C/h
Temperature.
Second step, builds single collimation of high stability, filtering divides amplitude grating writing system, by means of 325nmHe-
Interference fringe is written in holographic recording glass by designed screen periods with different uv-exposure dosage in Cd laser；The
Three steps generate permanent refractive index variation through Overheating Treatment, 510 DEG C of nucleation temperature, 535 DEG C of crystallization temperature, can prepare institute
The volume Bragg grating needed.
Embodiment 3
A kind of volume Bragg grating based on laser holographic recording glass, preparation method include step：
The first step, preparation group are divided into SiO260 parts, Na215 parts of O, 3 parts of ZnO, Al2O36 parts, 4 parts of NaF, KBr 3
Part, La2O32 parts, Ag20.1 part of O, Sb2O30.1 part, CeO20.03 part of laser holographic recording glass, is claimed by 1.4Kg
Amount proportion, Na2O is introduced in the form of sodium nitrate, B2O3It is introduced in the form of boric acid, Ag2O is introduced in the form of silver nitrate.It is melted
Process is by the way of secondary material, the quartz ceramic crucible that material is 1L using volume, 1220 DEG C by raw material gradually
It is added in the silica crucible by Elema heating, so that mixture is fused into glassy state, secondary material is at 1350 DEG C by glass
State holographic recording glass clinker is poured into batches in the pure platinum crucible of Φ 100mm × 100mm bore, is used according to specific technique
Platinum leaf slurry is stirred to carry out the clarification and homogenization of glass, and glass melting temperature is 1400 DEG C, melting time 12h, tapping temperature
1290 DEG C, high-temperature fusant is cast in 340 DEG C of 94 aluminium bronze molds at 1290 DEG C, after be transferred in annealing furnace, at 450 DEG C
Lower annealing 3h, is finally cooled to room temperature with the cooling rate of 4 DEG C/h.
Second step, builds single collimation of high stability, filtering divides amplitude grating writing system, by means of 325nmHe-
Interference fringe is written in holographic recording glass by designed screen periods with different uv-exposure dosage in Cd laser；The
Three steps generate permanent refractive index variation through Overheating Treatment, 430 DEG C of nucleation temperature, 510 DEG C of crystallization temperature, can prepare institute
The volume Bragg grating needed.
Embodiment 4
A kind of volume Bragg grating based on laser holographic recording glass, preparation method include step：
The first step, preparation group are divided into SiO262 parts, Na218 parts of O, 5 parts of ZnO, Al2O39 parts, 6 parts of NaF, KBr 5
Part, 5 parts of BaO, Ag20.2 part of O, Sb2O30.3 part, CeO20.05 part of laser holographic recording glass, is claimed by 1.4Kg
Amount proportion, Na2O is introduced in the form of sodium nitrate, B2O3It is introduced in the form of boric acid, Ag2O is introduced in the form of silver nitrate.It is melted
Process is by the way of secondary material, the quartz ceramic crucible that material is 1L using volume, 1240 DEG C by raw material gradually
It is added in the silica crucible by Elema heating, so that mixture is fused into glassy state, secondary material is at 1360 DEG C by glass
State holographic recording glass clinker is poured into batches in the pure platinum crucible of Φ 100mm × 100mm bore, is used according to specific technique
Platinum leaf slurry is stirred to carry out the clarification and homogenization of glass, and glass melting temperature is 1420 DEG C, melting time 5h, tapping temperature 1310
DEG C, high-temperature fusant is cast in 360 DEG C of 94 aluminium bronze molds at 1310 DEG C, after be transferred in annealing furnace, moved back at 470 DEG C
Fiery 6h is finally cooled to room temperature with the cooling rate of 6 DEG C/h.
Second step, builds single collimation of high stability, filtering divides amplitude grating writing system, by means of 325nmHe-
Cd laser designs screen periods with different uv-exposure dosage normally and interference fringe is written in holographic recording glass；The
Three steps generate permanent refractive index variation through Overheating Treatment, 530 DEG C of nucleation temperature, 540 DEG C of crystallization temperature, can prepare institute
The volume Bragg grating needed.
Embodiment 5
A kind of volume Bragg grating based on laser holographic recording glass, preparation method include step：
The first step, preparation group are divided into SiO261.6 parts, Na215 parts of O, 4 parts of ZnO, Al2O38 parts, 4.5 parts of NaF, KBr
3.5 parts, B2O33.2 parts, Ag20.07 part of O, Sb2O30.1 part, CeO20.03 part of laser holographic recording glass, by 1.4Kg
Carry out weighing proportion, Na2O is introduced in the form of sodium nitrate, B2O3It is introduced in the form of boric acid, Ag2O is drawn in the form of silver nitrate
Enter.Melting process is by the way of secondary material, and the quartz ceramic crucible that a material is 1L using volume will be former at 1230 DEG C
Material is gradually added in the silica crucible by Elema heating, so that mixture is fused into glassy state, secondary material is at 1350 DEG C
Glassy state holographic recording glass clinker is poured into batches in the pure platinum crucible of Φ 100mm × 100mm bore, according to specific work
Skill uses the stirring of platinum leaf slurry to carry out the clarification and homogenization of glass, and glass melting temperature is 1420 DEG C, melting time 6h, out furnace temperature
Degree 1300 DEG C, high-temperature fusant is cast in 350 DEG C of 94 aluminium bronze molds at 1300 DEG C, after be transferred in annealing furnace, 460
Anneal 2h at DEG C, is finally cooled to room temperature with the cooling rate of 5 DEG C/h.
Second step, builds single collimation of high stability, filtering divides amplitude grating writing system, by means of 325nmHe-
Interference fringe is written in holographic recording glass by designed screen periods with different uv-exposure dosage in Cd laser；The
Three steps generate permanent refractive index variation through Overheating Treatment, 510 DEG C of nucleation temperature, 535 DEG C of crystallization temperature, can prepare institute
The volume Bragg grating needed.
Embodiment 6
A kind of hologram pattern product based on laser holographic recording glass, preparation method includes step：
The first step, preparation group are divided into SiO261.6 parts, Na215 parts of O, 4 parts of ZnO, Al2O38 parts, 4.5 parts of NaF, KBr
3.5 parts, B2O33.2 parts, Ag20.07 part of O, Sb2O30.1 part, CeO20.03 part of laser holographic recording glass, by 1.4Kg
Carry out weighing proportion, Na2O is introduced in the form of sodium nitrate, B2O3It is introduced in the form of boric acid, Ag2O is drawn in the form of silver nitrate
Enter.Melting process is by the way of secondary material, and the quartz ceramic crucible that a material is 1L using volume will be former at 1230 DEG C
Material is gradually added in the silica crucible by Elema heating, so that mixture is fused into glassy state, secondary material is at 1350 DEG C
Glassy state holographic recording glass clinker is poured into batches in the pure platinum crucible of Φ 100mm × 100mm bore, according to specific work
Skill uses the stirring of platinum leaf slurry to carry out the clarification and homogenization of glass, and glass melting temperature is 1420 DEG C, melting time 6h, out furnace temperature
Degree 1300 DEG C, high-temperature fusant is cast in 350 DEG C of 94 aluminium bronze molds at 1300 DEG C, after be transferred in annealing furnace, 460
Anneal 2h at DEG C, is finally cooled to room temperature with the cooling rate of 5 DEG C/h.
Second step builds single collimation of high stability by required hologram pattern, filtering divides amplitude double light beam laser dry
Pattern writing system is related to, by means of 250-350nm wave band ultraviolet laser (such as 325nmHe-Cd laser), with certain purple
Interference fringe pattern is written in holographic recording glass in outer exposure dose；Third step generates permanent refractive index through Overheating Treatment
Variation, 510 DEG C of nucleation temperature, 535 DEG C of crystallization temperature, hologram pattern product required for can preparing.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can
With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention
Protect range.
Claims (8)
1. a kind of laser holographic recording glass, which is characterized in that by weight, including component：
2. laser holographic recording glass according to claim 1, which is characterized in that by weight, including component：
3. laser holographic recording glass according to claim 2, which is characterized in that by weight, including component：
4. a kind of preparation method of laser holographic recording glass as claimed in any one of claims 1 to 3, which is characterized in that institute
The preparation method for stating laser holographic recording glass includes step：
Accurate weighing raw material according to the ratio；
The fine grinding in mortar by raw material, makes its full and uniform mixing, and raw material is gradually added to stone at 1220~1240 DEG C
In English crucible, mixture is made to be fused into glassy state, obtains glassy state clinker；
Glassy state clinker is poured into platinum crucible in batches at 1350~1360 DEG C, stirring with carry out glass clarification and
Change, obtain high-temperature fusant, during which glass melting temperature is 1380~1420 DEG C, and melting time is 5~12h；
High-temperature fusant is transferred in 340~360 DEG C of copper mould at 1290~1310 DEG C, after be transferred in annealing furnace, 450
2~6h is kept the temperature at~470 DEG C, is finally at the uniform velocity cooled to room temperature, is obtained laser holographic recording glass.
5. the preparation method of laser holographic recording glass according to claim 4, which is characterized in that with the drop of 4~6 DEG C/h
Warm speed is cooled to room temperature, obtains laser holographic recording glass.
6. a kind of diffraction optical device or hologram pattern product, which is characterized in that using as described in any one of claims 1 to 3
Laser holographic recording glass be made.
7. the preparation method of a kind of diffraction optical device as claimed in claim 6 or hologram pattern product, which is characterized in that institute
The preparation method for stating diffraction optical device or hologram pattern product includes step：
Laser holographic recording glass is exposed, interference fringe is written by designed screen periods；
Laser holographic recording glass after exposure is heat-treated, permanent refractive index variation is generated, obtains diffraction optics device
Part or hologram pattern product, wherein heat treatment process includes nucleation and crystallization, and nucleation temperature is 430~530 DEG C, crystallization temperature
It is 510~540 DEG C.
8. the preparation method of diffraction optical device according to claim 7 or hologram pattern product, which is characterized in that use
The mode of black light interference exposure or femtosecond laser direct write is exposed laser holographic recording glass.
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| CN115432922A (en) * | 2022-08-31 | 2022-12-06 | 成都光明光电有限责任公司 | Photo-thermal conversion glass and preparation method thereof |
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