CN103496848A - Praseodymium-doped phosphate glass and method for preparing waveguides - Google Patents
Praseodymium-doped phosphate glass and method for preparing waveguides Download PDFInfo
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- CN103496848A CN103496848A CN201310422875.6A CN201310422875A CN103496848A CN 103496848 A CN103496848 A CN 103496848A CN 201310422875 A CN201310422875 A CN 201310422875A CN 103496848 A CN103496848 A CN 103496848A
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Abstract
The invention discloses praseodymium-doped phosphate glass and a method for preparing waveguides, and belongs to the technical field of rare earth-doped optical glass. The method comprises the following steps: firstly, after uniformly mixing a matrix raw material and praseodymium oxide, melting praseodymium-doped phosphate glass; then, preparing waveguides of the praseodymium-doped phosphate glass through an ion exchange method. According to the invention, the phosphate glass with excellent physical and chemical properties can be obtained by optimizing proportion of components the phosphate glass and improving the temperature system in a glass melting process so as to satisfy the demand on ion exchange. The waveguides of the praseodymium-doped phosphate glass capable of being efficiently coupled with visible single-mode and infrared single-mode optical fibers can be prepared by controlling the technical parameters such as ion exchange time and temperature. Plane waveguides which support multi-mode signal transmission are prepared. The maximum variation of the refractive index of the glass can reach 0.0083.
Description
Technical field
The invention belongs to rear-earth-doped opticglass technical field, be specifically related to a kind of praseodymium Doping Phosphorus hydrochlorate glass and prepare the method for waveguide.
Background technology
The integration that improves 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 to introduce rare earth element in waveguide, utilizes the energy level transition of rare earth element, and optical signal is amplified.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, aspect the waveguide type visible light source, having broad application prospects.
All the time, phosphate glass is difficult for occurring Fluorescence-quenching because having higher rare earth ion solubleness, 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, so the waveguide of praseodymium Doping Phosphorus hydrochlorate 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 Doping Phosphorus hydrochlorate glass and prepare the method for waveguide.At first by adjusting the glass ingredient proportioning, improve the temperature schedule of glass smelting process, obtain homogeneity and the good praseodymium Doping Phosphorus hydrochlorate glass of perviousness, then the praseodymium Doping Phosphorus hydrochlorate glass of excellent property of take is substrate, by ion exchange technique, acquisition can with the praseodymium Doping Phosphorus hydrochlorate 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 Doping Phosphorus hydrochlorate glass, prepared as follows by this praseodymium Doping Phosphorus hydrochlorate glass:
(1) by base starting material and Praseodymium trioxide (Pr
6o
11) be mixed to get compound; Wherein: described Praseodymium trioxide (Pr
6o
11) the amount 0.1～0.5wt% that is the 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 to 4～6 hours under 200～250 ℃ of conditions, naturally cools to room temperature, then be warming up to the glass metal that 1350 ℃ of insulations obtain melting in 0.5～1 hour; Again by the glass metal of melting through the die for molding of preheating, the glass after moulding is annealed 0.5～3 hour under 470～510 ℃ of conditions, makes praseodymium Doping Phosphorus hydrochlorate glass after naturally cooling to room temperature.
In above-mentioned steps (2), temperature rise rate is preferably 1～4 ℃/min; The preheating temperature of mould is preferably 470～510 ℃; Be preferably 5～30 minutes warm up time.
Utilize the method for above-mentioned praseodymium Doping Phosphorus hydrochlorate glass preparation waveguide, concrete steps are as follows:
After the described praseodymium Doping Phosphorus of I hydrochlorate glass carries out pre-treatment, be processed into the praseodymium Doping Phosphorus hydrochlorate glass substrate of desired size;
The II glass substrate, after cleaning, adopts the aluminium film of hot vapour deposition method at glass substrate surface evaporation thickness 150～200nm, then at glass substrate surface, opens the wide ion-exchange window of 4～50 μ m;
The glass substrate that III will have an ion-exchange window is immersed in 360～390 ℃ of saltpetre and carries out ion-exchange 0.5～2 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, clean again the aluminium film of glass substrate surface, obtain praseodymium Doping Phosphorus hydrochlorate glass waveguide after polishing.
Described in the step I, preprocessing process is: at first adopt silicon carbide to roughly grind processing to the praseodymium Doping Phosphorus hydrochlorate glass of preparation, and make its relative two sides parallel; Then adopt aluminum oxide to carry out fine grinding to glass, make its smooth surface; With polishing fluid, on polishing machine, to glass, carry out precise polished again; Finally with dehydrated alcohol, clean, make its surface cleaning.
The method of cleaning glass substrate in the step II is: glass substrate is placed in to trichloroethane, acetone and Virahol successively and respectively cleans 5～10min, finally with the remaining spot of deionized water rinsing, and with nitrogen, glass substrate surface is dried up.
Open the step of ion-exchange window at glass substrate surface in the step II as follows:
(a) utilize photoresist spinner to get rid of the SPR6112 positive photoetching rubber of a layer thickness 50～150nm at the glass substrate surface that is coated with the aluminium film, then will be covered with under 90 ℃ of the glass substrates of positive photoetching rubber baking 10 minutes;
(b) cover positive photoetching rubber quartz mask plate on the glass substrate after the baking, wide 4～50 μ m of striped, adopt lithography machine to expose under ultraviolet lamp 6～10 seconds, then the glass substrate after exposure is immersed in the AZ300MIF developing solution to 20～40 seconds, with distilled water, developing solution is rinsed well again, with this, at glass substrate surface, opened the wide ion-exchange window of 4～50 μ m;
(c) glass substrate that will open the ion-exchange window is placed in the mixed solution 4～20 minutes of phosphoric acid, acetic acid and nitric acid, and then the aluminium film on the deionizing exchanging window 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 has researched and developed broadband signal and has amplified with waveguide type praseodymium Doping Phosphorus hydrochlorate glass 1#, and selects unique feed composition proportioning, take that chemistry and thermal property are stablized and phosphoric acid salt with higher rare earth ion solubleness is main component.Pr
3+there is unique level structure, Pr
3+doping Phosphorus hydrochlorate glass～1.46 μ m near infrared emissions belong to
1d
2→
1g
4radiative transition, because of its large emission cross section and fluorescence halfwidth, can realize that E+S wave band optical signalling amplifies.
2, infrared single-mode fiber can be efficiently mated in praseodymium Doping Phosphorus hydrochlorate glass 1# of the present invention waveguide, realizes that E+S wave band optical signalling amplifies.
3, ion exchange technique is the promising waveguide fabrication technology of tool, but ion-exchange is normally carried out at higher temperature, the present invention is by optimizing the phosphate glass component proportion, improve the temperature schedule of glass smelting process, can obtain all good phosphate glasses of physicochemical property, thereby meet the needs of ion-exchange.Then by controlling the processing parameters such as ion-exchange time and temperature, prepared the praseodymium Doping Phosphorus hydrochlorate glass 1# slab guide of supporting the multimode signal transmission, the maximum change amount of its specific refractory power is up to 0.0083.
4, praseodymium Doping Phosphorus hydrochlorate glass 2# of the present invention has effective fluorescent emission in visibility region, and visible single-mode fiber can be efficiently mated in praseodymium Doping Phosphorus hydrochlorate glass 2# waveguide, as the waveguide type visible light source, uses.
5, the present invention passes through Al
2o
3introduce glass ingredient, in the time of the reinforcing glass physical strength, strengthened 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, make the setting rate of glass slack-off, improve its processability.
6, cost of material of the present invention is cheap, generally be easy to get, and suitable for mass production.
The 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 hydrochlorate glass 1# under 442nm excites.
Fig. 2 is monitoring 0.2wt%Pr
6o
11the excitation spectrum of the 1462nm emission peak of Doping Phosphorus hydrochlorate glass 1#.
Fig. 3 is 0.2wt%Pr
6o
11doping Phosphorus hydrochlorate 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 hydrochlorate glass 1# planar optical waveguide when lambda1-wavelength is 632.8nm.
Fig. 5 is 0.2wt%Pr
6o
11the mode profile of Doping Phosphorus hydrochlorate glass 1# planar optical waveguide when lambda1-wavelength is 1536nm.
Fig. 6 is 0.2wt%Pr
6o
11doping Phosphorus hydrochlorate glass 1# planar optical waveguide when lambda1-wavelength is 632.8nm with diffusion depth different index distribution situation.
Fig. 7 is 0.2wt%Pr
6o
11the near field mode chart of Doping Phosphorus hydrochlorate glass 1# single mode slab waveguide.
Fig. 8 is 0.2wt%Pr
6o
11the near field mode 3 D figure that Doping Phosphorus hydrochlorate glass 1# waveguide is 1550nm at lambda1-wavelength.
Fig. 9 is 0.2wt%Pr
6o
11the visible fluorescence spectrum of Doping Phosphorus hydrochlorate glass 2# under 443nm excites.
Figure 10 is monitoring 0.2wt%Pr
6o
11the excitation spectrum of the 598nm emission main peak of Doping Phosphorus hydrochlorate glass 2#.
Figure 11 is 0.2wt%Pr
6o
11doping Phosphorus hydrochlorate glass 2#'s
1d
2the fluorescence lifetime curve of energy level.
Figure 12 is 0.2wt%Pr
6o
11the mode profile of Doping Phosphorus hydrochlorate 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, obtain by commercial sources; The test methods such as the solution allocation of using, if no special instructions, be routine operation.
Below in conjunction with drawings and Examples in detail the present invention is described in detail.
(1) adopt following mole proportioning: 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, the above-mentioned base starting material of weighing, separately take the Praseodymium trioxide (Pr that accounts 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) will be placed in agate mortar by the raw material of the described method weighing of step (1) and fully mix, and pour platinum crucible into after it mixes, the chamber type electric resistance furnace that is placed in 230 ℃ is incubated 6 hours, with stove, is warming up under 1350 ℃ of conditions and is incubated half hour.
(3) glass metal of founding in step (2) is poured in 470 ℃ of lower preheatings rectangular aluminum die for molding of 5 minutes, by the 0.2wt%Pr after moulding
6o
11doping Phosphorus hydrochlorate glass 1# puts into 470 ℃ of resistance furnace annealing 3 hours, cools to room temperature with the furnace, to eliminate the internal stress of glass.
(4) after the glass prepared by step (3) takes out from resistance furnace, at first adopt silicon carbide by its double-side rough grinding processing, make the apparent surface parallel, adopt subsequently aluminum oxide to carry out fine grinding to glass, make its smooth surface, finally with polishing fluid, glass is carried out precise polishedly on polishing machine, and clean with dehydrated alcohol, make its surface cleaning.
(5) utilize Jobin Yvon Fluorolog-3 spectrophotometer, being equipped with near infrared R928 photomultiplier is that detector, commercial continuous wavelength xenon lamp are pumping source, the near-infrared fluorescent spectrum of glass sample under 442.0nm excites that record is 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 that E+S wave band optical signalling amplifies.
(6) employing and the identical means of testing of step (5), be equipped with the R928 photomultiplier, the excitation spectrum of glass sample prepared by minute book embodiment, and the monitoring wavelength is 1462.0nm, result is as Fig. 2.The spectrum of Fig. 2 has covered the continuous wavelength scope of 410-620nm, three excitation peaks that lay 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.The excitation spectrum explanation, this glass sample can effectively be excited by the multiple excitation light source of 410-620nm wavelength region.
(7) 0.2wt%Pr
6o
11doping Phosphorus hydrochlorate 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, can realize effective emission of praseodymium ion Doping Phosphorus hydrochlorate glass 1# under the exciting as commercial blue laser diode, blueness or blue-greenish colour photodiode and Argon ion laser.
(1) get 0.2wt%Pr
6o
11doping Phosphorus hydrochlorate 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 successively trichloroethane, acetone, Virahol, deionized water respectively to clean 5 minutes, then with nitrogen, substrate surface is dried up, standby.
(2) glass substrate, after cleaning, adopts the aluminium film of hot vapour deposition method at glass substrate surface evaporation thickness 150～200nm, then at glass substrate surface, opens the wide ion-exchange window of 4～50 μ m;
It is described that to open the step of ion-exchange window at glass substrate surface as follows:
(a) utilize 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 that is coated with the aluminium film, 60 seconds whirl coating time), then will be covered with under 90 ℃ of the glass substrates of positive photoetching rubber baking 10 minutes;
(b) cover positive photoetching rubber quartz mask plate on the glass substrate after the baking, wide 4～50 μ m of striped, adopt lithography machine to expose under ultraviolet lamp 6～10 seconds, then the glass substrate after exposure is immersed in the AZ300MIF developing solution to 20～40 seconds, with distilled water, developing solution is rinsed well again, with this, at glass substrate surface, opened the wide ion-exchange window of 4～50 μ m;
(c) glass substrate that will open the ion-exchange window is placed in the mixed solution 4～20 minutes (coming off to the aluminium film) of phosphoric acid, acetic acid and nitric acid, aluminium film on the deionizing exchanging window, then use organic solvent (as: Virahol) to wash away the photoresist material of glass substrate surface.
(3) will fill the saltpetre (KNO that purity is 99.99%
3) quartz crucible be placed in ion exchanging furnace, until temperature rise to 390 ℃ and stable after, the glass substrate that will process through step (1) be immersed in saltpetre 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, with deionized water, wash away the residual saltpetre of glass substrate surface, then clean the aluminium film of glass substrate surface, obtain 0.2wt%Pr after polishing
6o
11doping Phosphorus hydrochlorate glass 1# planar optical waveguide.
(4) 0.2wt%Pr that utilizes Metricon2010 prism-coupled instrument test procedure (3) to prepare
6o
11doping Phosphorus hydrochlorate 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 and the infrared single mode optical signal transmission that under the ion-exchange condition that this presentation of results adopts in step (3), prepare, if the ion-exchange waveguides of single mode signal transmission is supported in the wish preparation, can suitably shorten ion-exchange time.
(5) 0.2wt%Pr that employing IWKB(inverse Wentzel-Kramer-Brillouin) prepared by method matching step (3)
6o
11the index distribution situation (being showed in Fig. 6) of Doping Phosphorus hydrochlorate glass 1# planar optical waveguide different diffusion depths when lambda1-wavelength is 632.8nm, can draw to draw a conclusion: after ion-exchange, the ducting layer that thickness is about 8.8 μ m, waveguide surface specific refractory power (n have been formed at glass substrate surface
0) be 1.5223, substrate refractive index (n
sub) be 1.5140, therefore, the maximum change amount Δ n=n of specific refractory power
0-n
sub=0.0083, this value can be complementary with the specific refractory power of conventional single mode fiber, prove the optical waveguides for preparing by the present embodiment ion-exchange condition and with the optical fiber efficient coupling.
(6) incident light of 1.55 μ m is passed through to an end side surface of V-type groove fibre-optical fixator coupled into waveguide, opposite side end face in waveguide adopts a microcobjective that the light image of deriving in waveguide is passed to the charge-coupled device (CCD) photographic camera, thereby by the near field mode chart (Fig. 7) of deriving slab waveguide on computer and 3D figure (Fig. 8).By the near field mode chart, can be found out, glass waveguide is supported single mode transport at 1.5 μ m working frequency range, and its mode field diameter cross measures is 8.8 μ m, vertically is measured as 6.7 μ m, and this monomode optical waveguide and standard single-mode fiber have good crossover degree and repeatability.
Embodiment 3
(1) adopt following mole proportioning: 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, the above-mentioned base starting material of weighing, separately take the Praseodymium trioxide (Pr that accounts 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) will be placed in agate mortar by the raw material of the described method weighing of step (1) and fully mix, and pour platinum crucible into after it mixes, the chamber type electric resistance furnace that is placed in 230 ℃ is incubated 6 hours, with stove, is warming up under 1350 ℃ of conditions and is incubated half hour.
(3) glass metal of founding in step (2) is poured in 470 ℃ of lower preheatings rectangular aluminum die for molding of 5 minutes, by the 0.2wt%Pr after moulding
6o
11doping Phosphorus hydrochlorate glass 2# puts into 510 ℃ of resistance furnace annealing 3 hours, cools to room temperature with the furnace, to eliminate the internal stress of glass.
(4) after the glass prepared by step (3) takes out from resistance furnace, at first adopt silicon carbide by its double-side rough grinding processing, make relative surface parallel, adopt subsequently aluminum oxide to carry out fine grinding to glass, make its smooth surface, finally with polishing fluid, glass is carried out precise polishedly on polishing machine, and clean with dehydrated alcohol, make its surface cleaning.
(5) utilize Jobin Yvon Fluorolog-3 spectrophotometer, being equipped with the R928 photomultiplier is that detector, commercial continuous wavelength xenon lamp are pumping source, the glass sample visible fluorescence spectrum 443.0nm excite under of record after step (4) is processed, 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) employing and the identical means of testing of step (5), minute book embodiment prepares the excitation spectrum of glass sample, and the 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 can effectively be excited by the multiple excitation light source of 410-620nm wavelength region, as Argon ion laser, blue or glaucous photodiode etc.
(7) employing and the identical means of testing of step (5), being equipped with xenon flash lamp is pumping source, 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%, has disclosed and has started from
1d
2effective emission of energy level is hopeful to obtain.
(1) choose the 0.2wt%Pr of embodiment 3 preparations
6o
11doping Phosphorus hydrochlorate glass 2#, its processing is processed into 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 successively trichloroethane, acetone and Virahol respectively to clean 10 minutes, then with washed with de-ionized water, with nitrogen, substrate surface is dried up again, standby.
(2) glass substrate, after cleaning, adopts the aluminium film of hot vapour deposition method at glass substrate surface evaporation thickness 150～200nm, then at glass substrate surface, opens the wide ion-exchange window of 4～50 μ m (method is with embodiment 2);
(3) will fill the saltpetre (KNO that purity is 99.99%
3) quartz crucible be placed in ion exchanging furnace, until temperature rise to 390 ℃ and stable after, the glass substrate that will process through step (2) be immersed in saltpetre 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, with deionized water, wash away the residual saltpetre of glass substrate surface, then clean the aluminium film of glass substrate surface, obtain 0.2wt%Pr after polishing
6o
11doping Phosphorus hydrochlorate glass 2# planar optical waveguide.
(4) utilizing planar optical waveguide prepared by Metricon2010 prism-coupled instrument test procedure (3) 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 optical signal transmission of optical waveguides support prepared under the ion-exchange condition that this presentation of results adopts in step (3).
Above-described embodiment is that the present invention is preparing preferably embodiment of waveguide type praseodymium Doping Phosphorus hydrochlorate glass; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (9)
1. a praseodymium Doping Phosphorus hydrochlorate glass, it is characterized in that: the preparation method of described praseodymium Doping Phosphorus hydrochlorate glass comprises the steps:
(1) base starting material and Praseodymium trioxide are mixed to get to compound; Wherein: 0.1～0.5wt% that the amount of described Praseodymium trioxide is the 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 to 4～6 hours under 200～250 ℃ of conditions, naturally cools to room temperature, then be warming up to the glass metal that 1350 ℃ of insulations obtain melting in 0.5～1 hour; Again by the glass metal of melting through the die for molding of preheating, the glass after moulding is annealed 0.5～3 hour under 470～510 ℃ of conditions, makes praseodymium Doping Phosphorus hydrochlorate glass after naturally cooling to room temperature.
2. praseodymium Doping Phosphorus hydrochlorate glass according to claim 1 is characterized in that: in described step (2), temperature rise rate is 1～4 ℃/min.
3. praseodymium Doping Phosphorus hydrochlorate glass according to claim 1, it is characterized in that: described in described step (2), mould is aluminium-making mould.
4. praseodymium Doping Phosphorus hydrochlorate glass according to claim 1, is characterized in that: 470～510 ℃ of the preheating temperatures of mould described in described step (2).
5. praseodymium Doping Phosphorus hydrochlorate glass according to claim 1, is characterized in that: 5～30 minutes described warm up time.
6. utilize the method for praseodymium Doping Phosphorus hydrochlorate glass preparation waveguide claimed in claim 1, it is characterized in that: concrete steps are as follows:
After the described praseodymium Doping Phosphorus of I hydrochlorate glass carries out pre-treatment, be processed into the praseodymium Doping Phosphorus hydrochlorate glass substrate of desired size;
The II glass substrate, after cleaning, adopts the aluminium film of hot vapour deposition method at glass substrate surface evaporation thickness 150～200nm, then at glass substrate surface, opens the wide ion-exchange window of 4～50 μ m;
The glass substrate that III will have an ion-exchange window is immersed in 360～390 ℃ of saltpetre and carries out ion-exchange 0.5～2 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, clean again the aluminium film of glass substrate surface, obtain praseodymium Doping Phosphorus hydrochlorate glass waveguide after polishing.
7. the method for preparing waveguide according to claim 6, it is characterized in that: described in the step I, preprocessing process is: at first adopt silicon carbide to roughly grind processing to the praseodymium Doping Phosphorus hydrochlorate glass of preparation, and make its relative two sides parallel; Then adopt aluminum oxide to carry out fine grinding to glass, make its smooth surface; With polishing fluid, on polishing machine, to glass, carry out precise polished again; Finally with dehydrated alcohol, clean, make its surface cleaning.
8. the method for preparing waveguide according to claim 6, it is characterized in that: the method for cleaning glass substrate in the step II is: glass substrate is placed in to trichloroethane, acetone and Virahol successively and respectively cleans 5～10min, finally with the remaining spot of deionized water rinsing, and with nitrogen, glass substrate surface is dried up.
9. the method for preparing waveguide according to claim 6 is characterized in that: open the process steps of ion-exchange window at glass substrate surface in described step II as follows:
(a) utilize photoresist spinner to get rid of the SPR6112 positive photoetching rubber of a layer thickness 50～150nm at the glass substrate surface that is coated with the aluminium film, then will be covered with under 90 ℃ of the glass substrates of positive photoetching rubber baking 10 minutes;
(b) cover positive photoetching rubber quartz mask plate on the glass substrate after the baking, wide 4～50 μ m of striped, adopt lithography machine to expose under ultraviolet lamp 6～10 seconds, then the glass substrate after exposure is immersed in the AZ300MIF developing solution to 20～40 seconds, with distilled water, developing solution is rinsed well again, with this, at glass substrate surface, opened the wide ion-exchange window of 4～50 μ m;
(c) glass substrate that will open the ion-exchange window is placed in the mixed solution 4～20 minutes of phosphoric acid, acetic acid and nitric acid, and then the aluminium film on the deionizing exchanging window washes away the photoresist material of glass substrate surface with organic solvent.
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| CN110133798A (en) * | 2019-07-02 | 2019-08-16 | 山东大学 | The method that ridge optical waveguide is prepared using diamond dicing saw |
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