CN103496848B - A kind of praseodymium doped phosphate glass and prepare the method for waveguide - Google Patents
A kind of praseodymium doped phosphate glass and prepare the method for waveguide Download PDFInfo
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- CN103496848B CN103496848B CN201310422875.6A CN201310422875A CN103496848B CN 103496848 B CN103496848 B CN 103496848B CN 201310422875 A CN201310422875 A CN 201310422875A CN 103496848 B CN103496848 B CN 103496848B
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- praseodymium
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- 229910052777 Praseodymium Inorganic materials 0.000 title claims abstract description 59
- 239000005365 phosphate glass Substances 0.000 title claims abstract description 42
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000011521 glass Substances 0.000 claims abstract description 100
- 238000005342 ion exchange Methods 0.000 claims abstract description 43
- 239000007858 starting material Substances 0.000 claims abstract description 11
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 68
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 239000004323 potassium nitrate Substances 0.000 claims description 10
- 235000010333 potassium nitrate Nutrition 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001259 photo etching Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229920002120 photoresistant polymer Polymers 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000001459 lithography Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 9
- 230000008054 signal transmission Effects 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 4
- 238000010168 coupling process Methods 0.000 abstract description 4
- 238000005859 coupling reaction Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 238000010309 melting process Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 description 25
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 23
- 229910052698 phosphorus Inorganic materials 0.000 description 23
- 239000011574 phosphorus Substances 0.000 description 23
- 239000005368 silicate glass Substances 0.000 description 23
- 239000002994 raw material Substances 0.000 description 7
- 230000007704 transition Effects 0.000 description 6
- 238000000695 excitation spectrum Methods 0.000 description 5
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 description 5
- -1 rare earth ions Chemical class 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 241001460678 Napo <wasp> Species 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 230000011664 signaling Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 1
- 150000001213 Praseodymium Chemical class 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
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- Glass Compositions (AREA)
Abstract
The invention discloses the preparation method of a kind of praseodymium doped phosphate glass and the waveguide of praseodymium doped phosphate glass, belong to rear-earth-doped opticglass technical field.First praseodymium doped phosphate glass is founded after base starting material and Praseodymium trioxide being mixed; Then the waveguide of praseodymium doped phosphate glass is prepared by ion exchange method.The present invention, by optimizing phosphate glass component proportion, improves the temperature schedule of glass melting process, can obtain the phosphate glass that physicochemical property is all good, thus meet the needs of ion-exchange.Then by controlling the processing parameter such as ion-exchange time and temperature, preparation can with the praseodymium doped phosphate glass waveguide of visible single mode and infrared single-mode fiber efficient coupling, and prepared the slab guide supporting multimode signal transmission, the maximum knots modification of its specific refractory power is up to 0.0083.
Description
Technical field
The invention belongs to rear-earth-doped opticglass technical field, be specifically related to a kind of praseodymium doped phosphate glass and prepare the method for waveguide.
Background technology
The integration improving optics is one of focus of optical communication field research all the time.Fiber waveguide device is as the important primary element of optical communication device, and it amplifies mechanism is introduce rare earth element in the waveguide, utilizes the energy level transition of rare earth element, amplifies optical signal.Therefore find suitable glass host material, obtain the optical amplifier of high gain, wide bandwidth, compact type, its operation wavelength is very important to zone spreading beyond C-band.
In addition, the superfluorescence that fiber waveguide device produces has very strong directivity, and the rare earth ions such as samarium, europium, praseodymium all have effective fluorescent emission in visibility region, and can realize the efficient coupling with optical fiber, therefore, have broad application prospects in waveguide type visible light source.
All the time, not easily there is Fluorescence-quenching because having higher solubilize rare earth ions degree in phosphate glass, is considered to the substrate material of good optical communication device.Through K
+-Na
+the waveguide of ion-exchange phosphate glass shows lower surface scattering loss, symmetrical index distribution and the compatibility good with single-mode fiber, therefore the waveguide of praseodymium doped phosphoric acid salt is urgently studied in the application in the fields such as communication, illumination and waveguide type visible light source.
Summary of the invention
The object of the present invention is to provide a kind of praseodymium doped phosphate glass and prepare the method for waveguide.First by adjustment glass ingredient proportioning, improve the temperature schedule of glass melting process, obtain homogeneity and the good praseodymium doped phosphate glass of perviousness, then with the praseodymium doped phosphate glass of excellent property for substrate, by ion exchange technique, obtain can with the praseodymium doped phosphate glass waveguide of visible single mode and infrared single-mode fiber efficient coupling.
For achieving the above object, technical solution of the present invention is as follows:
A kind of praseodymium doped phosphate glass, this praseodymium doped phosphate glass is prepared as follows:
(1) by base starting material and Praseodymium trioxide (Pr
6o
11) be mixed to get compound; Wherein: described Praseodymium trioxide (Pr
6o
11) amount be 0.1 ~ 0.5wt% of base starting material total amount, described base starting material is sodium-metaphosphate, magnesium metaphosphorate, aluminium metaphosphate and aluminum oxide, and its molar ratio is: sodium-metaphosphate: magnesium metaphosphorate: aluminium metaphosphate: aluminum oxide=50 ~ 67:3 ~ 4:25 ~ 44:3 ~ 4;
(2) step (1) gained compound is incubated 4 ~ 6 hours under 200 ~ 250 DEG C of conditions, naturally cools to room temperature, be then warming up to the glass metal that 1350 DEG C of insulations obtain melting for 0.5 ~ 1 hour; Again by the glass metal of melting in the die for molding through preheating, the glass after shaping is annealed 0.5 ~ 3 hour under 470 ~ 510 DEG C of conditions, naturally cools to obtained praseodymium doped phosphate glass after room temperature.
In above-mentioned steps (2), temperature rise rate is preferably 1 ~ 4 DEG C/min; The preheating temperature of mould is preferably 470 ~ 510 DEG C; Be preferably 5 ~ 30 minutes warm up time.
Utilize above-mentioned praseodymium doped phosphate glass to prepare the method for waveguide, concrete steps are as follows:
After praseodymium doped phosphate glass carries out pre-treatment described in I, be processed into the praseodymium doped phosphate glass substrate of desired size;
II glass substrate, after cleaning, adopts hot vapour deposition method at the aluminium film of glass substrate surface evaporation thickness 150 ~ 200nm, then opens the ion-exchange window of 4 ~ 50 μm wide at glass substrate surface;
The glass substrate with ion-exchange window to be immersed in 360 ~ 390 DEG C of saltpetre and to carry out ion-exchange 0.5 ~ 2 hour by III, glass substrate is taken out after ion-exchange, naturally cool to room temperature, the residual saltpetre of glass substrate surface is washed away with deionized water, clean the aluminium film of glass substrate surface again, after polishing, obtain the waveguide of praseodymium doped phosphate glass.
Preprocessing process described in step I is: first adopt the praseodymium doped phosphate glass of silicon carbide to preparation to carry out corase grind processing, and make its relative two sides parallel; Then adopt aluminum oxide to carry out fine grinding to glass, make its smooth surface; Carry out precise polished to glass with polishing fluid on polishing machine again; Last with washes of absolute alcohol, make its surface cleaning.
The method of cleaning glass substrate in step II is: glass substrate is placed in successively trichloroethane, acetone and Virahol respectively cleaning 5 ~ 10min, finally with deionized water rinsing residual soil, and is dried up by glass substrate surface with nitrogen.
The step of ion-exchange window is opened at glass substrate surface as follows in step II:
A () utilizes photoresist spinner to get rid of the SPR6112 positive photoetching rubber of a layer thickness 50 ~ 150nm at the glass substrate surface being coated with aluminium film, then by be covered with positive photoetching rubber glass substrate 90 DEG C at baking 10 minutes;
B the glass substrate after () baking covers positive photoetching rubber quartz mask plate, striped is wide 4 ~ 50 μm, lithography machine is adopted to expose 6 ~ 10 seconds under ultraviolet lamp, then the glass substrate after exposure to be immersed in AZ300MIF developing solution 20 ~ 40 seconds, with distilled water, developing solution is rinsed well again, open the ion-exchange window of 4 ~ 50 μm wide with this at glass substrate surface;
C the glass substrate opening ion-exchange window is placed in the mixed solution 4 ~ 20 minutes of phosphoric acid, acetic acid and nitric acid by (), the aluminium film on deionizing exchanging window, then washes away the photoresist material of glass substrate surface with organic solvent.
Beneficial effect of the present invention is as follows:
1, the present invention have developed broadband signal amplification waveguide type praseodymium doped phosphate glass 1#, and selects unique feed composition proportioning, stablize with chemistry and thermal property and the phosphoric acid salt with higher solubilize rare earth ions degree for main component.Pr
3+there is unique level structure, Pr
3+doping Phosphorus silicate glass ~ 1.46 μm of near infrared emissions belong to
1d
2→
1g
4radiative transition, the emission cross section large because of it and fluorescence halfwidth, can realize E+S wave band optical signalling and amplify.
2, praseodymium doped phosphate glass 1# of the present invention waveguide can the infrared single-mode fiber of efficient matchings, realizes E+S wave band optical signalling and amplifies.
3, ion exchange technique is the promising waveguide manufacturing technologies of most, but ion-exchange is normally carried out at a higher temperature, the present invention is by optimizing phosphate glass component proportion, improve the temperature schedule of glass melting process, the phosphate glass that physicochemical property is all good can be obtained, thus meet the needs of ion-exchange.Then by controlling the processing parameter such as ion-exchange time and temperature, prepared the praseodymium doped phosphate glass 1# slab guide supporting multimode signal transmission, the maximum knots modification of its specific refractory power is up to 0.0083.
4, praseodymium doped phosphate glass 2# of the present invention has effective fluorescent emission in visibility region, and praseodymium doped phosphate glass 2# waveguide can the visible single-mode fiber of efficient matchings, uses as waveguide type visible light source.
5, the present invention passes through Al
2o
3introduce glass ingredient, while reinforcing glass physical strength, enhance the acid resistance of glass matrix, solve the problem of the easy acid corrosion of glass matrix in ion exchange process; By introducing a small amount of MgO, making the setting rate of glass slack-off, improving its processability.
6, low in raw material price of the present invention, is generally easy to get, suitable for mass production.
Accompanying drawing explanation
Accompanying drawing 12 width of the present invention.
Fig. 1 is 0.2wt%Pr
6o
11the Infrared fluorescence spectrum of Doping Phosphorus silicate glass 1# under 442nm excites.
Fig. 2 is monitoring 0.2wt%Pr
6o
11the excitation spectrum of the 1462nm emission peak of Doping Phosphorus silicate glass 1#.
Fig. 3 is 0.2wt%Pr
6o
11doping Phosphorus silicate glass 1# belongs to
1d
2→
1g
4the stimulated emission cross section of energy level transition.
Fig. 4 is 0.2wt%Pr
6o
11the mode profile of Doping Phosphorus silicate glass 1# planar optical waveguide when lambda1-wavelength is 632.8nm.
Fig. 5 is 0.2wt%Pr
6o
11the mode profile of Doping Phosphorus silicate glass 1# planar optical waveguide when lambda1-wavelength is 1536nm.
Fig. 6 is 0.2wt%Pr
6o
11doping Phosphorus silicate glass 1# planar optical waveguide when lambda1-wavelength is 632.8nm with the index distribution situation that diffusion depth is different.
Fig. 7 is 0.2wt%Pr
6o
11the near field mode chart of Doping Phosphorus silicate glass 1# single mode slab waveguide.
Fig. 8 is 0.2wt%Pr
6o
11the near field mode 3 D that Doping Phosphorus silicate glass 1# waveguide is 1550nm at lambda1-wavelength schemes.
Fig. 9 is 0.2wt%Pr
6o
11the visible fluorescence spectrum of Doping Phosphorus silicate glass 2# under 443nm excites.
Figure 10 is monitoring 0.2wt%Pr
6o
11the 598nm of Doping Phosphorus silicate glass 2# launches the excitation spectrum of main peak.
Figure 11 is 0.2wt%Pr
6o
11doping Phosphorus silicate glass 2#'s
1d
2the fluorescence lifetime curve of energy level.
Figure 12 is 0.2wt%Pr
6o
11the mode profile of Doping Phosphorus silicate glass 2# planar optical waveguide when lambda1-wavelength is 632.8nm.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Agents useful for same in following embodiment, if no special instructions, obtains by commercial sources; The test methods such as the solution allocation used, if no special instructions, are routine operation.
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
Embodiment 1
(1) following mol ratio is adopted: sodium-metaphosphate (NaPO
3): magnesium metaphosphorate (Mg (PO
3)
2): aluminium metaphosphate (Al (PO
3)
3): aluminum oxide (Al
2o
3)=67:4:25:4, weighs above-mentioned base starting material, separately takes the Praseodymium trioxide (Pr accounting for base starting material total amount 0.2wt%
6o
11) as doping agent, the purity of all raw materials is 99.99%, specifically prepare burden in table one.
Table one
| Raw material | NaPO 3 | Mg(PO 3) 2 | Al(PO 3) 3 | Al 2O 3 | Pr 6O 11 |
| Weight (g) | 10.787 | 1.151 | 10.418 | 0.644 | 0.046 |
(2) raw material weighed by the described method of step (1) is placed in agate mortar fully to mix, after it mixes, pours platinum crucible into, the chamber type electric resistance furnace being placed in 230 DEG C is incubated 6 hours, is incubated half hour under being warming up to 1350 DEG C of conditions with stove.
(3) glass metal founded in step (2) is poured into the preheating rectangular aluminum die for molding of 5 minutes at 470 DEG C, by the 0.2wt%Pr after shaping
6o
11doping Phosphorus silicate glass 1# puts into 470 DEG C of resistance furnace annealing 3 hours, cools to room temperature with the furnace, to eliminate the internal stress of glass.
(4) after glass prepared by step (3) being taken out from resistance furnace, first silicon carbide is adopted to be processed by its double-side rough grinding, make apparent surface parallel, aluminum oxide is adopted to carry out fine grinding to glass subsequently, make its smooth surface, finally carry out precise polished to glass with polishing fluid on polishing machine, and with washes of absolute alcohol, make its surface cleaning.
(5) JobinYvonFluorolog-3 spectrophotometer is utilized, be equipped with that near infrared R928 photomultiplier is detector, commercial continuous wavelength xenon lamp is pumping source, record the near-infrared fluorescent spectrum of glass sample under 442.0nm excites processed through step (4), result is as Fig. 1.As seen from Figure 1, the emission peak that this glass sample is positioned at 1462.0nm comes from praseodymium ion
1d
2→
1g
4radiative transition, fluorescence halfwidth (FWHM) is 113nm, makes it can realize E+S wave band optical signalling and amplifies.
(6) adopt the means of testing identical with step (5), be equipped with R928 photomultiplier, the excitation spectrum of glass sample prepared by minute book embodiment, monitoring wavelength is 1462.0nm, and result is as Fig. 2.The spectrum of Fig. 2 covers the continuous wavelength scope of 410-620nm, three excitation peaks laying respectively at 442.0nm, 472.0nm and 589.0nm be due to praseodymium ion by
3h
4ground state level to (
3p
2,
1i
6), (
3p
1,
3p
0) and
1d
2the transition of energy level causes.Excitation spectrum illustrates, this glass sample effectively can be excited by the multiple excitation light source of 410-620nm wavelength region.
(7) 0.2wt%Pr
6o
11doping Phosphorus silicate glass 1# belongs under 442.0nm excites
1d
2→
1g
4the stimulated emission cross section of energy level transition, result is as Fig. 3.In Fig. 3, the maximum stimulated emission cross section in 1468.0nm place is 1.1 × 10
-20cm
2, show under suitable shooting conditions, effective transmitting of praseodymium ion Doping Phosphorus silicate glass 1# under the exciting as commercial blue laser diode, blueness or blue-greenish colour photodiode and Argon ion laser, can be realized.
Embodiment 2
(1) 0.2wt%Pr is got
6o
11doping Phosphorus silicate glass 1#, be processed into that to be of a size of 3.0cm × 1.8cm × 0.3cm(long × wide × thick) and the smooth glass substrate of two-sided parallel surfaces, adopt trichloroethane, acetone, Virahol, deionized water respectively to clean 5 minutes successively, then with nitrogen, substrate surface is dried up, for subsequent use.
(2) glass substrate is after cleaning, adopts hot vapour deposition method at the aluminium film of glass substrate surface evaporation thickness 150 ~ 200nm, then opens the ion-exchange window of 4 ~ 50 μm wide at glass substrate surface;
It is described that to open the step of ion-exchange window at glass substrate surface as follows:
A () utilizes photoresist spinner to get rid of SPR6112 positive photoetching rubber (the rotating speed 2000rpm of photoresist spinner rotation mantle of a layer thickness 50 ~ 150nm at the glass substrate surface being coated with aluminium film, 60 seconds whirl coating time), then by be covered with positive photoetching rubber glass substrate 90 DEG C at baking 10 minutes;
B the glass substrate after () baking covers positive photoetching rubber quartz mask plate, striped is wide 4 ~ 50 μm, lithography machine is adopted to expose 6 ~ 10 seconds under ultraviolet lamp, then the glass substrate after exposure to be immersed in AZ300MIF developing solution 20 ~ 40 seconds, with distilled water, developing solution is rinsed well again, open the ion-exchange window of 4 ~ 50 μm wide with this at glass substrate surface;
C the glass substrate opening ion-exchange window is placed in the mixed solution 4 ~ 20 minutes (coming off to aluminium film) of phosphoric acid, acetic acid and nitric acid by (), aluminium film on deionizing exchanging window, then uses organic solvent (as: Virahol) to wash away the photoresist material of glass substrate surface.
(3) saltpetre (KNO that purity is 99.99% will be filled
3) quartz crucible be placed in ion exchanging furnace, after temperature rises to 390 DEG C and be stable, be immersed in saltpetre by the glass substrate processed through step (1) and carry out ion-exchange and prepare planar optical waveguide, ion-exchange time is 0.5 hour.Take out glass substrate after ion-exchange, naturally cool to room temperature, wash away the residual saltpetre of glass substrate surface with deionized water, then clean the aluminium film of glass substrate surface, after polishing, obtain 0.2wt%Pr
6o
11doping Phosphorus silicate glass 1# planar optical waveguide.
(4) 0.2wt%Pr prepared by Metricon2010 prism-coupled instrument test procedure (3) is utilized
6o
11doping Phosphorus silicate glass 1# planar optical waveguide is 632.8nm(Fig. 4 at lambda1-wavelength) and 1536nm(Fig. 5) time mode profile.This planar optical waveguide has two integrated patterns and an imperfect pattern when lambda1-wavelength is 632.8nm; When lambda1-wavelength is 1536nm, there is an integrated pattern on surface.The visible multimode of optical waveguides support that this result is prepared under the ion exchange conditions adopted in step (3) is described and infrared single-mode optics Signal transmissions, if support the ion-exchange waveguides of single mode signal transmission for preparation, then suitably can shorten ion-exchange time.
(5) IWKB(inverseWentzel-Kramer-Brillouin is adopted) 0.2wt%Pr for preparing of method fit procedure (3)
6o
11the index distribution situation (being showed in Fig. 6) of Doping Phosphorus silicate glass 1# planar optical waveguide different diffusion depth when lambda1-wavelength is 632.8nm, can draw to draw a conclusion: after ion-exchange, the ducting layer that thickness is about 8.8 μm is defined, waveguide surface specific refractory power (n at glass substrate surface
0) be 1.5223, substrate refractive index (n
sub) be 1.5140, therefore, the maximum knots modification Δ n=n of specific refractory power
0-n
sub=0.0083, this value can match with the specific refractory power of conventional single mode fiber, prove the optical waveguides prepared by the present embodiment ion exchange conditions and with optical fiber efficient coupling.
(6) by the one end side of the incident light of 1.55 μm by V-type groove fibre-optical fixator coupled into waveguide, adopt a microcobjective that charge-coupled device (CCD) photographic camera is passed in the light image of deriving in waveguide at the opposite side end face of waveguide, thus scheme (Fig. 8) by the near field mode chart (Fig. 7) and 3D of computer being derived slab waveguide.As can be seen near field mode chart, glass waveguide supports single mode transport at 1.5 μm of working frequency range, and its mode field diameter cross measures is 8.8 μm, and be longitudinally measured as 6.7 μm, this monomode optical waveguide and standard single-mode fiber have good crossover degree and repeatability.
Embodiment 3
(1) following mol ratio is adopted: sodium-metaphosphate (NaPO
3): magnesium metaphosphorate (Mg (PO
3)
2): aluminium metaphosphate (Al (PO
3)
3): aluminum oxide (Al
2o
3)=50:3:44:3, weighs above-mentioned base starting material, separately takes the Praseodymium trioxide (Pr accounting for base starting material total amount 0.2wt%
6o
11) as doping agent, the purity of all raw materials is 99.99%, specifically prepare burden as table two.
Table two
| Raw material | NaPO 3 | Mg(PO 3) 2 | Al(PO 3) 3 | Al 2O 3 | Pr 6O 11 |
| Weight (g) | 6.677 | 0.716 | 15.207 | 0.401 | 0.046 |
(2) raw material weighed by the described method of step (1) is placed in agate mortar fully to mix, after it mixes, pours platinum crucible into, the chamber type electric resistance furnace being placed in 230 DEG C is incubated 6 hours, is incubated half hour under being warming up to 1350 DEG C of conditions with stove.
(3) glass metal founded in step (2) is poured into the preheating rectangular aluminum die for molding of 5 minutes at 470 DEG C, by the 0.2wt%Pr after shaping
6o
11doping Phosphorus silicate glass 2# puts into 510 DEG C of resistance furnace annealing 3 hours, cools to room temperature with the furnace, to eliminate the internal stress of glass.
(4) after glass prepared by step (3) being taken out from resistance furnace, first silicon carbide is adopted to be processed by its double-side rough grinding, make relative surface parallel, aluminum oxide is adopted to carry out fine grinding to glass subsequently, make its smooth surface, finally carry out precise polished to glass with polishing fluid on polishing machine, and with washes of absolute alcohol, make its surface cleaning.
(5) JobinYvonFluorolog-3 spectrophotometer is utilized, be equipped with that R928 photomultiplier is detector, commercial continuous wavelength xenon lamp is pumping source, record the visible fluorescence spectrum of glass sample under 443.0nm excites after step (4) process, the results are shown in Fig. 9.Be that the visible fluorescence emission peak of this glass sample lays respectively at 480.0nm, 597.0nm and 690.0nm as seen from Figure 9.
(6) adopt the means of testing identical with step (5), minute book embodiment prepares the excitation spectrum of glass sample, and monitoring wavelength is 598.0nm, and result is as Figure 10.Its three excitation peak summits lay respectively at 443.0nm, 468.0nm and 480.0nm, and this shows that this sample effectively can be excited by the multiple excitation light source of 410-620nm wavelength region, as Argon ion laser, and blue or glaucous photodiode etc.
(7) adopt the means of testing identical with step (5), being equipped with xenon flash lamp is pumping source, and minute book embodiment prepares praseodymium ion in glass sample
1d
2the fluorescence lifetime curve of energy level, result is as Figure 11.Obtain praseodymium ion
1d
2the quantum yield of energy level is 87.7%, discloses and starts from
1d
2effective transmitting of energy level is hopeful to obtain.
Embodiment 4
(1) 0.2wt%Pr prepared by embodiment 3 is chosen
6o
11doping Phosphorus silicate glass 2#, processed and be processed into that to be of a size of 3.0cm × 1.8cm × 0.3cm(long × wide × thick) and the smooth glass substrate of two-sided parallel surfaces, trichloroethane, acetone and Virahol is adopted respectively to clean 10 minutes successively, then with washed with de-ionized water, with nitrogen, substrate surface is dried up again, for subsequent use.
(2) glass substrate is after cleaning, adopts hot vapour deposition method at the aluminium film of glass substrate surface evaporation thickness 150 ~ 200nm, then opens the ion-exchange window (method is with embodiment 2) of 4 ~ 50 μm wide at glass substrate surface;
(3) saltpetre (KNO that purity is 99.99% will be filled
3) quartz crucible be placed in ion exchanging furnace, after temperature rises to 390 DEG C and be stable, be immersed in saltpetre by the glass substrate processed through step (2) and carry out ion-exchange and prepare planar optical waveguide, ion-exchange time is 2 hours.Take out glass substrate after ion-exchange, naturally cool to room temperature, wash away the residual saltpetre of glass substrate surface with deionized water, then clean the aluminium film of glass substrate surface, after polishing, obtain 0.2wt%Pr
6o
11doping Phosphorus silicate glass 2# planar optical waveguide.
(4) planar optical waveguide utilizing Metricon2010 prism-coupled instrument test procedure (3) to prepare is 632.8nm(Figure 12 at lambda1-wavelength) time mode profile.This planar optical waveguide has an integrated pattern and an imperfect pattern when lambda1-wavelength is 632.8nm.The visible single-mode optics Signal transmissions of optical waveguides support that this result is prepared under the ion exchange conditions adopted in step (3) is described.
Above-described embodiment is that the present invention is at preparation waveguide type praseodymium doped phosphate glass preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a praseodymium doped phosphate glass, is characterized in that: the preparation method of described praseodymium doped phosphate glass comprises the steps:
(1) base starting material and Praseodymium trioxide are mixed to get compound; Wherein: the amount of described Praseodymium trioxide is 0.1 ~ 0.5wt% of base starting material amount, described base starting material is sodium-metaphosphate, magnesium metaphosphorate, aluminium metaphosphate and aluminum oxide, and its molar ratio is: sodium-metaphosphate: magnesium metaphosphorate: aluminium metaphosphate: aluminum oxide=50 ~ 67:3 ~ 4:25 ~ 44:3 ~ 4;
(2) step (1) gained compound is incubated 4 ~ 6 hours under 200 ~ 250 DEG C of conditions, naturally cools to room temperature, be then warming up to the temperature rise rate of 1 ~ 4 DEG C/min the glass metal that 1350 DEG C of insulations obtain melting for 0.5 ~ 1 hour; Again by the glass metal of melting in the die for molding through 470 ~ 510 DEG C of preheatings, the glass after shaping is annealed 0.5 ~ 3 hour under 470 ~ 510 DEG C of conditions, naturally cools to obtained praseodymium doped phosphate glass after room temperature.
2. praseodymium doped phosphate glass according to claim 1, is characterized in that: described in described step (2), mould is aluminium-making mould.
3. praseodymium doped phosphate glass according to claim 1, is characterized in that: 5 ~ 30 minutes described warm up time.
4. utilize the praseodymium doped phosphate glass described in claim 1 to prepare the method for waveguide, it is characterized in that: concrete steps are as follows:
After praseodymium doped phosphate glass carries out pre-treatment described in I, be processed into the praseodymium doped phosphate glass substrate of desired size;
II glass substrate, after cleaning, adopts hot vapour deposition method at the aluminium film of glass substrate surface evaporation thickness 150 ~ 200nm, then opens the ion-exchange window of 4 ~ 50 μm wide at glass substrate surface;
The glass substrate with ion-exchange window to be immersed in 360 ~ 390 DEG C of saltpetre and to carry out ion-exchange 0.5 ~ 2 hour by III, glass substrate is taken out after ion-exchange, naturally cool to room temperature, the residual saltpetre of glass substrate surface is washed away with deionized water, clean the aluminium film of glass substrate surface again, after polishing, obtain the waveguide of praseodymium doped phosphate glass.
5. the method preparing waveguide according to claim 4, is characterized in that: preprocessing process described in step I is: first adopt the praseodymium doped phosphate glass of silicon carbide to preparation to carry out corase grind processing, and make its relative two sides parallel; Then adopt aluminum oxide to carry out fine grinding to glass, make its smooth surface; Carry out precise polished to glass with polishing fluid on polishing machine again; Last with washes of absolute alcohol, make its surface cleaning.
6. the method preparing waveguide according to claim 4, it is characterized in that: the method for cleaning glass substrate in step II is: glass substrate is placed in successively trichloroethane, acetone and Virahol respectively cleaning 5 ~ 10min, last with deionized water rinsing residual soil, and with nitrogen, glass substrate surface is dried up.
7. the method preparing waveguide according to claim 4, is characterized in that: open the process steps of ion-exchange window at glass substrate surface in described step II as follows:
A () utilizes photoresist spinner to get rid of the SPR6112 positive photoetching rubber of a layer thickness 50 ~ 150nm at the glass substrate surface being coated with aluminium film, then by be covered with positive photoetching rubber glass substrate 90 DEG C at baking 10 minutes;
B the glass substrate after () baking covers positive photoetching rubber quartz mask plate, striped is wide 4 ~ 50 μm, lithography machine is adopted to expose 6 ~ 10 seconds under ultraviolet lamp, then the glass substrate after exposure to be immersed in AZ300MIF developing solution 20 ~ 40 seconds, with distilled water, developing solution is rinsed well again, open the ion-exchange window of 4 ~ 50 μm wide with this at glass substrate surface;
C the glass substrate opening ion-exchange window is placed in the mixed solution 4 ~ 20 minutes of phosphoric acid, acetic acid and nitric acid by (), the aluminium film on deionizing exchanging window, then washes away the photoresist material of glass substrate surface with organic solvent.
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