ZA200403772B - A process of making rare earth doped optical fibre. - Google Patents
A process of making rare earth doped optical fibre. Download PDFInfo
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- ZA200403772B ZA200403772B ZA200403772A ZA200403772A ZA200403772B ZA 200403772 B ZA200403772 B ZA 200403772B ZA 200403772 A ZA200403772 A ZA 200403772A ZA 200403772 A ZA200403772 A ZA 200403772A ZA 200403772 B ZA200403772 B ZA 200403772B
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- silica
- core
- tube
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- 238000000034 method Methods 0.000 title claims description 129
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 110
- 150000002910 rare earth metals Chemical class 0.000 title claims description 85
- 239000013307 optical fiber Substances 0.000 title claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 109
- 239000006185 dispersion Substances 0.000 claims description 45
- 239000000835 fiber Substances 0.000 claims description 44
- 239000000377 silicon dioxide Substances 0.000 claims description 42
- 238000005245 sintering Methods 0.000 claims description 37
- 239000010410 layer Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 30
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000002105 nanoparticle Substances 0.000 claims description 24
- 239000002019 doping agent Substances 0.000 claims description 22
- 238000000527 sonication Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000012792 core layer Substances 0.000 claims description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000007796 conventional method Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000005350 fused silica glass Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 8
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000005253 cladding Methods 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 238000011161 development Methods 0.000 claims description 4
- 238000003618 dip coating 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
- 230000000994 depressogenic effect Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 101100520660 Drosophila melanogaster Poc1 gene Proteins 0.000 claims 1
- 101100520662 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PBA1 gene Proteins 0.000 claims 1
- 238000007596 consolidation process Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- -1 rare earth halides Chemical class 0.000 description 25
- 239000004071 soot Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 238000001704 evaporation Methods 0.000 description 13
- 238000010348 incorporation Methods 0.000 description 13
- 229910052691 Erbium Inorganic materials 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 7
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical compound CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 description 4
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 101000998969 Homo sapiens Inositol-3-phosphate synthase 1 Proteins 0.000 description 2
- 102100036881 Inositol-3-phosphate synthase 1 Human genes 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002123 erbium compounds Chemical class 0.000 description 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CTCOPPBXAFHGRB-UHFFFAOYSA-N ethanolate;germanium(4+) Chemical compound [Ge+4].CC[O-].CC[O-].CC[O-].CC[O-] CTCOPPBXAFHGRB-UHFFFAOYSA-N 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 239000000146 host glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000008774 maternal effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910003451 terbium oxide Inorganic materials 0.000 description 1
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
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- Glass Compositions (AREA)
Description
. © WO 03/033423 PCT/IN01/00184
A PROCESS OF MAKING RARE EARTH DOPED OPTICAL FIBRE
Technical Field . The present invention relates to a Process of Making Rare Earth Doped Optical Fibre.
Background Art ’ High silica based optical fibres are firmly established as the most efficient interconnection media for optical telecommunication networks. The fibres are used as the passive transmission media to guide optical signals over long distances. In contrast, rare-earth (RE) ions if doped into the core of such fibres, make them optically active due to the characteristic emission of the RE when pumped at suitable wavelengths. Because of this property RE doped fibres have shown great potential for use as active devices for photonic applications like optical amplifiers and fibre lasers at various wavelengths. The fibres are also found to be promising candidates for their application as sensors for monitoring temperature, radiation dose etc.
Erbium doped fiber which is the active medium of an EDFA (erbium doped fiber amplifier) has been an enabling technology for optical networks operating in the third telecommunication window between 1530 and 1610 nm. EDFA can simultaneously amplify several optical channels in a single fibre which has enabled the implementation of
DWDM (dense wavelength division multiplexing) technology with the potential of increasing the bandwidth of long distance transmission systems from Gb/s to Tb/s ranges.
EDFAs exhibit high gain, large bandwidth, low noise, polarisation insensitive gain, substantially reduced cross talk problems and low insertion losses at the operating wavelengths. The deployment of EDFA has spurred a tremendous growth in advanced telecommunication systems replacing the conventional optoelectronic repeaters.
While the Erbium Doped Fibre (EDF) remains the most important for telecommunication applications, fibres doped with other rare earths are gaining importance mostly for development of laser sources from visible to mid infrared regions. Development of , broadband amplifiers commencing from 1300 nm is an area of great interest using various
REs. Lasing and amplification have been demonstrated at several wavelengths with the . 30 incorporation of the various rare-earths.
Reference may be made to Townsend J.E., Poole S.B., and Payne D.N., Electronics Letters,
Vol. 23 (1987) p-329, ¢ Solution-doping technique for fabrication of rare-earth-doped optical fibre’ wherein the Modified Chemical Vapour Deposition (MCVD) process is used to fabricate the preform with a step index profile and desired core-clad structure while solution doping is adopted for incorporation of the active ion. The steps involed in the process are as follows: e A conventional cladding doped with P,O; and F is deposited within a high silica glass substrate tube to develop matched clad or depressed clad type structure. eo The core layers of predetermined composition containing index raising dopant like .
GeO, are deposited at a lower temperature to form unsintered porous soot. ® The tube with the deposit is immersed into an aqueous solution of the dopant precursor (typical concentration 0.1 M) up to 1 hour. Any soluble form of the dopant ion is suitable for preparation of the solution although rare earth halides have been mostly used. e Following immersion, the tube is rinsed with acetone and remounted on lathe. e The core layer containing the RE is dehydrated and sintered to produce a clear glassy layer. Dehydration is carried out a temperature of 600°C by using chlorine. The level of
OH is reduced below 1ppm using Cl, / O, in the ratio of 5:2, provided the drying time exceeds 30 min. e Collapsing in the usual manner to produce a solid glass rod called preform. e Fibre drawing is conventional.
Reference may also be made to DiGiovanni D.J .» SPIE Vol. 1373 (1990) p-2 “Fabrication of rare-earth-doped optical fibre’ wherein the substrate tube with the porous core layer is soaked in an aqueous or alcoholic solution containing a nitrate or chloride of the desired
RE ion. The tube is drained, dried and remounted on lathe. The dehydration is carried out by flowing dry chlorine through the tube at about 900°C for an hour. After dehydration, the layer is sintered and the tube is collapsed to be drawn to fibre.
Reference may also be made to Ainslie B.J., Craig S.P., Davey S.T., and Wakefield B.,
Maternal Letters, Vol. 6, (1988) p-139, “ The fabrication, assessment and optical properties of high- concentration Nd*>* and Er** doped silica based fibres” wherein optical fibres based on ALO, - P,O;. - SiO, host glass doped with high concentrations of Nd** and Er** , have been fabricated by solution method and quantified. Following the deposition of cladding layers P,O4 doped silica soot is deposited at lower temperature. The prepared . tubes are soaked in an alcoholic solution of IM AI(NO,); + various concentrations of
ErCl; and NdCl, for 1 hour. The tubes are subsequently blown dry and collapsed to make preforms in the usual way. Aluminium (Al) is said to be a key component in producing high RE concentrations in the core centre without clustering effect. It is further disclosed
: © WO 03/033423 PCT/IN01/00184 that Al and RE profile lock together in some way which retards the volatility of RE ion.
The dip at the core centre is observed both for P and GeO, .
Reference may also be made to US Patent No. 5,005,175 (1991) by Desuvire et al., ‘Erbium doped fiber amplifier” wherein the fibre for the optical amplifier comprises a . 5 single mode fibre doped with erbium in the core having a distribution profile of the RE ion whose radius is less than 1.9 um while the radius of the mode of the pump signal exceeds 3 pm. The numerical aperture (NA) of the fibres varies from 0.2 to 0.35 and the core is doped with both Al and Ge oxides to increase the efficiency. The fibre with such design is reported to have increased gain and lower threshold compared to the conventional Er doped fibre amplifiers.
Reference may also be made to US Patent No. 5,778,129 (1998) by Shukunami et. al., ‘Doped optical fibre having core and clad structure for increasing the amplification band of an optical amplifier using the optical fibre’ wherein the porous core layer is deposited after developing the cladding inside a quartz tube by MCVD process and solution doping method is employed to impregnate Er as the active ion into the porous core to be followed by vitrification and collapsing for making the preform. The solution also contain compounds of Al, say chlorides, for co-doping of the core with Al in order to expand the amplification band. The Er and Al doped glass constitutes first region of the core.
Surrounding this are the second and third regions of the core. The third region contains Ge to increase the refractive index. The second region has an impurity concentration lower than both those of first and third regions and consequently low RI also. The second region acts as a barrier to prevent diffusion of the active dopant.
Reference may also be made to US Patent No. 5474588 (1995) by Tanaka, D. et. al,, ‘Solution doping of a silica with erbium, aluminium and phosphorus to form an optical fiber’ wherein a manufacturing method for Er doped silica is described in which silica glass soot is deposited on a seed rod (VAD apparatus) to form a porous soot preform, dipping the said preform into an ethanol solution containing an erbium compound, an ) aluminium compound and a phosphoric ester, and desiccating said preform to form Er, Al and P containing soot preform. The desiccation is carried out for a period of 24 -240 hours at a temperature of 60° - 70 °C in an atmosphere of nitrogen gas or inert gas. This desiccated soot preform is heated and dehydrated for a period of 2.5 - 3.5 hours at a temperature of 950° - 1050 °C in an atmosphere of helium gas containing 0.25 to 0.35% chlorine gas and further heated for a period of 3-5 hours at a temperature of 1400° - 1600°C to render it transparent, thereby forming an erbium doped glass preform. The segregation of
AICI; in the preform formation process is suppressed due to the presence of phosphorus and as a result, the doping concentration of Al ions can be set to a high level (>3 wt%). The dopant concentration and component ratio of Er, Al and P ions are claimed to be extremely accurate and homogeneous in radial as well as in longitudinal directions. .
Reference may also be made to US Patent No. 5123940 (1992) by DiGiovanni et. al., ‘Sol-
Gel doping of optical fibre preform’ wherein the method comprises collapsing a silica - based glass tube to make a preform and drawing fibre from the preform. Before collapsing the tube, one or more glass layers are formed in the inner surface of the glass tube by dip- coating with a stable dispersion (sol) containing the metal-alkoxides and dopant. cations including RE-ions. The metal-alkoxides dissolved in an alcoholic or aquous solvent contains required quantity of the dopants, polymerising the sol to form a gel, drying and sintering the tube. A wide variety of dopant materials, in the form of salts or alkoxides are easily incorporated by dissolving them in the solvent. The method suffers disadvantage that there is a possibility of evaporation of the RE-salts during sintering at high temperature, there by causing inhomogeneous distribution of RE-ions through out the length of the preform.
Reference may also be made to the publication by Matejec et al., ‘Properties of optical fibre preforms prepared by inner coating of substrates tubes’ Ceramics-Silicaty, 45 (2), 62 (2001) wherein the method consists of collapsing a silica based glass tube containing the required dopant cations to a preform and drawing fibre from the preform. Before collapsing the tube, one or more glass layers are formed in the inner surface of the glass tube by raising and lowering the sol level at a fixed velocity. The sol contained the silicon tetracthoxide (TEOS) and dopant cations including RE-ions. The TEOS dissolved in an alcoholic or aqueous solvent contains required quantity of the dopants, polymerizing the sol to form a gel followed by drying and sintering the tube. The main disadvantage of the method is that there is every possibility of evaporation of the RE salts during sintering at high temperature, resulting in an inhomogeneous distribution of RE-ions throughout the ' length of the preform.
A few of the drawbacks of the above mentioned processes are as follows: 1. Deposition of porous silica soot layer at a temperature of 1200 - 1400 °C by Chemical
Vapour Deposition (CVD) process inside a substrate silica tube or on a seed rod ( VAD or OVD apparatus).
: © WO 03/033423 PCT/IN01/00184 2. The porosity of the soot layer controls the RE incorporation and the homogeneity along the length of the preform. 3. The control of porosity of the deposited unsintered layer is difficult as it is extremely sensitive to the deposition temperature, burner traverse speed and flow of the reactant . 5 materials. This leads to variation in soot density and composition along the length of the tube. 4. The dipping procedure of the soot containing preform into the RE solution is critical due to the possibility of generation of local imperfections and concentration variation in the core of the preform. 5. Minor variation in dipping parameters coupled with the porosity of the unsintered soot layer leads to considerable change in RE concentration as well as radial distribution in the core of the preform. 6. The dipping parameters and the porosity of the soot layer are critical to obtain good core-clad interface and minimise attenuation of the fibre. 157. The dopant materials are concentrated in the pores of the deposited layer, As a result, clusters or microcryastallites of dopants tend to form both before sintering and during the steps of sintering and collapsing of the glass materials, giving rise to inhomogenuous distribution of the dopant materials. 8. Formaton of microcrystallites causes scattering of light and increases the attenuation of the fibre. 9. Evaporation of the solvent leaves behind a residue containing the salt of the dopant cations or RE oxychloride which during dehydration in the chlorine atmosphere or sintering at high temperature volatilises, creating a dip in concentration near the inner surface of the porous layer. 10. Dehydration and sintering of the RE chloride impregnated soot layer give rise to compositional variation due to the vaporization of the dopant salt as well as GeO, in the core. ) 11. The process suffers from reliability / repeatability due to its sensitivity to the parameters during various stages of processing such as deposition, solution doping, drying and sintering.
Objects of the invention:
The main object of the present invention is to provide a process for making rare earth doped optical fibre which obviates the drawbacks as detailed above.
Another object of the present invention is to provide a method of fabricating RE doped preforms and optical fibres by using RE coated silica nanoparticles as precursors.
Still another object of the present invention is to prepare RE (Er, Nd, Fu etc.) coated silica nanoparticles by a known technique. (Ref: ‘Sonochemical Preparation and Characterization of Eu;03 and Tb03 Doped 1n and Coated on Silica and Alumina Nanoparticles’, A.Patra, ,
E. Sominska, S. Ramesh, Yu. Koltypin, Z. Zhong, H. Minti, R. Reisfeld and A. Gedanken,
J. Phys. Chem. B, Vol 103 (17) pp 3361-3365).
Yet another object of the present invention is to disperse the rare-earth coated silica nanoparticles in sol under sonication containing germanium tetraethoxide and aluminium salt.
Still another object of the present invention is to control the viscosity of the sol and apply a sol-gel thin film inside high purity silica glass tube by the dip coating technique.
Yet another object of the present invention is to optimize the lifting speed for controlling the thickness of the coating to maintain the desired clad-core dimensions in the preform.
Still another object of the present invention is to control the viscosity of the sol, pH and the lifting speed to obtain homogeneous and uniform coating along the length of the tube.
Yet another object of the present invention is to optimize the loading percentage of the nanoparticles and other codopants in the sol.
Still another object of the present invention is to reduce the possibility of change in composition of the particulate core layer due to evaporation of the RE salt during drying and sintering .
Yet another object of the present invention is to produce preforms with desired RE concentration in the core and good homogeneity along the length of the preform.
Still another object of the present invention is to reduce the time period of processing the silica tube at high temperature for fabrication of RE doped preforms.
Yet another object of the present invention is to reduce the number of steps of the process to make the process more simple and economic.
Still another object of the present invention is to process the tube at ambient temperature ’ before sintering and collapsing instead of high temperature involved in the CVD process to . make it more simple and economic.
Yet another object of the present invention is to reduce the requirement of precision equipments for fabrication and consequently reduce the capital investment and cost of the product.
: © WO 03/033423 : PCT/IN01/00184
Still another object of the present invention is to provide a process where the numerical aperture of the fibre is varied from 0.10 to 0.30 maintaining RE concentration in the core between 50 to 5000 ppm along to produce fibres suitable for application as amplifiers, fibre lasers and sensors for different purposes. . 5 Yet another object of the present invention is to make the process less sensitive to the process parameters and consequently make it more reliable and economic.
The novelty of the present invention lies in eliminating the step of the formation of porous soot layer at high temperature (1000°C or above) by CVD process inside a fused silica glass tube for formation of the core. Instead a thin silica gel coating containing other dopants in desired proportions is applied through a silica sol at ambient temperature. The above method ensures a better control of the characteristics of the coated layer and uniformity along the length of the tube. The inventive step further includes elimination of the step of the incorporation of the rare-earth ions into the porous soot layer following the solution-doping technique. The rare-earth oxide coated silica nanoparticles are dispersed at ambient temperature in the silica sol mentioned above under sonication thereby further eliminating the formation of microcrystallites and clusters of rare-earth ions. The elimination of the possibility of evaporation of RE salts at high temperatures due to the direct addition of RE oxides is another inventive step of the process which prevents change in composition including variation of RE concentration in the core and also reduces the possibility of formation of RE dip at the core centre. The RE incorporation effficiency is much higher than the conventional processes. The process thus ensures better control of RE concentration in the doped region and homogeneous distribution of RE ions along the radial direction as well as the longitudinal direction. As a result the reproducibilty and reliability of the process increase to a great extent. The addition of Ge(OET), at ambient temperature in the silica sol above reduces the quantity of GeCly which is required at high temperature to achieve the desired NA. All the steps combined make the process simple ' and more economic than the conventional processes.
Accordingly, the present invention provides a process of making rare earth doped optical fibre which comprises (a) obtaining rare earth oxide coated (Eu,03, Nd,Qs, Tb0s, Er,O; etc.) silica nanoparticles by sonochemical method, (b) preparation of stable dispersions of the above RE containing powders in the desired proportion in presence of suitable dopants like Al;O3, GeO, etc. in a silica sol of Si(OC;Hs)s under sonication, (c) applying a thin coating of the silica sol on the inner surface of high purity clear fused silica glass tubes by sol-gel dip coating technique, (d) drying the coated layer in air at 70 to 150°C, (e) mounting the tube on glass working lathe for processing by MCVD technique, ® dehydrating the coated layer inside the tube at a temperature in the range of 800-1200 °C in . presence of excess Cl, (g) sintering the coated layer in presence of a mixture of oxygen and helium in the temperature range of 1400 to 1800°C for formation of the core, (h) collapsing the tube by usual method at a temperature in the range of 2000-2300 °C to obtain a preform, (i) overcladding the preform with silica tube and (j) drawing fibres of standard dimensions from the preform by the conventional methods.
In an embodiment of the present invention, the RE oxide is selected from Eu,03, Nd,0s,
Tb,03 and Er,O3 for preparation of the silica nanoparticles.
In another embodiment of the present invention, P,O, and F doped synthetic cladding is deposited within a silica glass substrate tube prior to development of the coating by known method like Modified Chemical Vapour Deposition (MCVD) process to obtain matched or depressed clad type structure in the preform.
In a further embodiment of the present invention, particle size of the RE coated SiO, powders ranges from 50 to 200 nm.
In still another embodiment of the present invention, the composition in oxide mol% of
SiO; : RE;Os in REO; coated SiO, powders varies from 99.5: 0.5 to 95 : 5.
In yet another embodiment of the present invention, the equivalent oxide mol% of SiO; in the dispersion varies from 98.5 to 90.5.
In still another embodiment of the present invention, a silica sol prepared with Si(OC;Hs), was used as the diluent of the RE,O; coated silica powder.
In yet another embodiment of the present invention, the equivalent oxide mol% of GeO, in the dispersion varies from 1.0 to 5.0.
In still another embodiment of the present invention, GeO, was added through Ge(OC;Hs)4 in the silica sol. ‘
In yet another embodiment of the present invention, the equivalent oxide mol% of Al,O; in the . dispersion ranges from 0.5 to 4.0.
In further embodiment of the present invention, Al,O; is provided to the solvent in the form of aluminium salts such as chlorides, nitrates or any other salt soluble in the solvent.
In yet another embodiment of the present invention, the solution of aluminium salt is prepared using a solvent selected from alcohol and water.
: © WO 03/033423 PCT/IN01/00184
In still another embodiment of the present invention, the oxide mol% of REO; in the dispersion ranges from 0.01 to 0.60. i In yet another embodiment of the present invention, strong mineral acids used for preparing the sol for dispersion are selected from hydrochloric or nitric acid. . 5 In still another embodiment of the present invention, the alcohol selected is soluable in the dispersion system.
In yet another embodiment of the present invention, the alcohol is selected from the group comprising of methyl alcohol, ethyl alcohol, propan-1-ol, propan-2-ol, butan-1-ol and butan-2-ol.
In yet another embodiment of the present invention, pH of the dispersion ranges from 1 to 5.
In still another embodiment of the present invention viscosity of the dispersion varies from 1 to 10 mPa s.
In yet another embodiment of the present invention sonication time of the dispersion ranges from 30 to 200 minutes.
In still another embodiment of the present invention settling time of the dispersion varies from 1 to 10 hours.
In yet another embodiment of the present invention lifting speed of the tube from the dispersion ranges from 4 to 15 cm/min.
In still another embodiment of the present invention baking temperature of the coated tube varies from 70° to 150°C.
In yet another embodiment of the present invention baking time of the coated tube ranges from 0.5 to 5 h.
In still another embodiment of the present invention the core composition is selected from the group comprising of RE;O3; +Si0;+Ge0O;, RE;03; +Si0;+GeO; +Al;03, RE;O3 +Si0,+Ge0; +A1,0; +P;0s and REO; +Si0,+GeO; + POs.
In still another embodiment of the present invention the temperature of the RE oxide ! containing core layer is increased in steps of 50 to 200°C during sintering depending on the composition and AI/RE concentration of the core layer.
In yet another embodiment of the present invention, the mixture of O, and He is in the range of 3:1 to 9:1 during sintering.
In still another embodiment of the present invention, source of chlorine is CCl, where helium is used as carrier gas.
In yet another embodiment of the present invention, the proportion of Cl,: O, during drying varies from 1.5: 1t0 3.5: 1.
In still another embodiment of the present invention, the dehydration period lies between 1 to 2 hours.
In yet another embodiment of the present invention, the core layer is sintered in the } presence of germania to facilitate germania incorporation and to obtain appropriate numerical aperture value.
In still another embodiment of the present invention, germama is supplied to the core layer during sintering by including GeCl, with the input oxygen.
In another embodiment of the present invention, the sintering is carried out at a temperature of 1200°C to 1400°C.
In yet another embodiment of the present invention, depending on the composition of the core, POCI; is added to the input gas mixture during sintering.
In another embodiment of the present invention, the core layer is doped with P,Os to facilitate RE incorporation.
In still another embodiment of the present invention P,O, and GeO, concentrations vary from 0.5 to 5.0 mol% and 3.0 to 25.0 mol% respectively in the RE doped core layer of the preform.
In yet another embodiment of the present invention the numerical aperture of the fibre is varied from 0.10 to 0.30.
In another embodiment of the present invention, RE concentration in the core is maintained in the range of 50 to 4000 ppm to produce fibres suitable for application as amplifiers, fibre lasers and sensors or different purposes.
In a further embodiment of the present invention, codopants like Al and other rare earths are added to the core doped with a selected RE to fabricate fibres containing various dopants in the core in the concentration range of 50 to 5000 ppm and numerical aperture varying between 0.10 and 0.30.
In still another embodiment of the present invention the deposition of a porous soot layer at high temperature (1000°C or above) by CVD process inside a fused silica glass tube or on a . seed rod (VAD or OVD apparatus) is eliminated for formation of the core.
In yet another embodiment of the present invention better control is achieved over the characteristics of the coated layer like porosity, thickness etc. and uniformity along the length of the tube.
: © WO 03/033423 PCT/INO1/00184
In still another embodiment of the present invention the difficulties and uncertainties involved in incorporation of the rare-earth ions in desired concentration into the porous soot layer by the solution-doping technique and such other methods are eliminated.
In still another embodiment of the present invention the rare-earth oxide coated silica . 5 nanoparticles are dispersed at ambient temperature in the silica sol mentioned above under sonication thereby eliminating the possibility of formation of the microcrystallites and clusters of rare-earth ions as in the conventional techniques.
In yet another embodiment of the present invention the possibility of evaporation of RE salts at high temperatures is considerably eliminated due to the direct addition of RE oxides which prevents change in composition including variation of RE concentration in the core and also reduces the possibility of formation of RE dip at the core centre.
In still another embodiment of the present invention the process ensures better control of
RE concentration in the doped region and homogeneous distribution of RE ions along the radial direction as well as throughout the length of the preform.
In yet another embodiment of the present invention the RE incorporation efficiency is much higher compared to the conventional techniques beacuse of direct addition of the RE oxides into the dispersion instead of the corresponding salt by the conventional techniques thereby minimising the possibility of evaporation and change in concentration.
In still another embodiment of the present invention the addition of Ge(OC,Hjs), at ambient temperature in the silica sol above reduces the quantity of GeCls which is required at high temperature to achieve the desired NA.
In yet another embodiment of the present invention the time period of processing the silica tube at high temperature and the number of steps involved for doping of RE ions by the conventional techniques for fabrication of the preform are considerably reduced.
In still another embodiment of the present invention the processing of the tube at ambient temperature before sintering and collapsing instead of high temperature involved in the
CVD process makes the process less sensitive to the process parameters unlike the conventional processes. ] In still another embodiment of the present invention the advantages described above increases the reproducibilty and reliability of the process to a great extent.
In yet another embodiment of the present invention the requirement of precision equipments for control of porous soot deposition, RE incorporation etc. during fabrication of the preform is considerably eliminated which will reduce the capital investment and cost of the product.
In still another embodiment of the present invention the advantages combined make the process simple and more economic than the conventional processes.
Figure 1 & 2 represent respectively the spectral attenuation curve of Er doped fibre prepared from RE doped nanoparticles following the present process and that fabricated by conventional solution doping technique.
Figure 3 & 4 show the refractive index profiles of Er doped fibre prepared through nanoparticle route and that by solution doping method respectively.
The invention is further explained with the help of following examples which should not be construed to limit the scope of the invention:
Sonochemical preparation of RE»O;- coated silica nanoparticles following the process mentioned in the Ref: ‘Sonochemical Preparation and
Characterization of Eu;O3; and Tb,O; Doped in and Coated on Silica and Alumina
Nanoparticles’ A.Patra, E. Sominska, S. Ramesh, Yu. Koltypin, Z. Zhong, H. Minti, R.
Reisfeld and A. Gedanken, J. Phys. Chem. B, Vol 103 (17) pp 3361-3365. (It does not form a part of the invention ) :
Amorphous silica microspheres in the size range of 50-250 nm were synthesized by the alkaline hydrolysis of tetraethoxysilane (Stober method). For the preparation of the
RE;O3- coated silica nangparticles with molar composition (100-x)SiO;-xRE;0;, nanophased rare earth oxides were sonochemically deposited on the outer surface of spherical silica particles. For this purpose, rare earth nitrate used as the source of rare earth was prepared by dissolving rare earth oxide in a minimum amount of nitric acid followed by evaporating it to dryness. The dry nitrate was dissolved in calculated quantity of water to prepare the rare earth nitrate solution.
The required amount of silica microspheres was taken in a beaker and calculated quantity of water and rare earth nitrate solution, as prepared earlier, were then added to it. The open beaker with the material was kept in an ice-bath and subjected to sonication for 1h employing a direct immersion titanium horn (Vibracell, 20 kHz, 100 W/cm?) Required ] amount of 25% aqueous ammonia was thereafter added in drops into the beaker during sonication. The resulting product after sonication was washed thoroughly with water, centrifuged and finally dried under vacuum to obtain RE coated amorphous silica nanoparticles.
The above method is also suitable for the preparation of doped and co-doped silica particles containing Al,O3, GeO;, Yb,0; and other rare earth oxides.
EXAMPLE 1 : Er-doped fibre e¢ Amorphous silica microspheres synthesized by hydrolysis of tetraethoxyorthosilicate (Stober method) were dispersed in a solution of erbium nitrate (kept in an ice bath) in a proportion of 98.5 mol% SiO; and 1.5 mol% Er,O3 under sonication followed by the addition of aqueous ammonia by known process. The resulting product was washed with water followed by centrifugation and drying under vacuum. e A stable dispersion of composition 94.985i10,:3Ge0,:2A1,05: 0.02Er,0; (in equivalent oxide mol%) was prepared for the application of coating to the inner wall of high purity clear fused silica glass tubes. e From the erbium oxide (Er,0;3) coated silica powders with 98.5 mol% SiO; and 1.5 mol% Er;Os, a silica sol of composition of 94.98 equivalent mol% of SiO, and 0.02 equivalent mol% of Er,O; was prepared by diluting with a slica sol containing the desired amount of silicon tetracthoxide (TEOS). e Silica-germania sol containing 3 equivalent oxide mol% of germanium ethoxide [Ge(OC,Hs)4] was prepared through the hydrolysis of TEOS and [Ge(OC;Hs)4] with water and hydrochloric acid in presence of a mixed solvent of propan-1-ol and butan- 2-ol. pH of the above sol was 1.5 + 0.05 . e 2 equivalent oxide mol% of [AlI(NO3)3.9H,0] and 0.02 equivalent mol% of Er,Os through Er,O; coated SiO; powders (after baking at 100°C for 1h) were dispersed in the above silica sol under sonication (26 kHz) for 80 mins. e The resultant dispersion after allowing to settle for 2 h, was used to coat the inner wall of the throughly cleaned silica glass tubes with inner diameter of 17.8 mm. The outer / wall of the tubes were properely masked with a suitable substance (parafilm). eo Coating was performed by dipping the silica glass tubes with a speed of 8 cm/min into the dispersion and lifting the same tube from the above dispersions with the same speed. e The coated tubes were dried in air at 100°C for 1h. e Oxidation at temperatures of 660°, 750°, 850° and 940°C with 2 passes of the burner at each temperature maintaining a constant He/O, ratio of 1:5 .
e The dehydration was carried out at a temperature of 930°C with a Cl,: O, ratio of 2.25 : 1 for a period of one hour. . e For sintering the temperature was increased in 3 steps up to 1220°C, each step consisting of 2 passes of the burner. GeCl, was added in controlled quantities during this stage with the input oxygen with two passes at 1220°C and one pass at 1425°C in : order to adjust the NA of the preform / fibre. eo The tube was further heated to increase the temperature stepwise to 1650°C for complete sintering of the Ge, Er & Al containing coated layer. During sintering O, and
He flow was in the ratio of of 5:1. eo The collapsing was done in 3 steps in the usual manner with positive oxygen pressure of 4 psi inside the tube to avoid any deformation in shape or geometry and excessive evaporation of GeO, or other oxides from the core. e Overcladding was done to reduce the core:clad ratio to 3.4:125. The NA measured in " the fibre was 0.21 £0.01 . eo The Er” ion concentration in the fibre was 220 ppm approx. as measured from the absorption at selected wavelengths.
EXAMPLE 2
Nd-doped fibre eo Amorphous silica microspheres synthesized by hydrolysis of tetraethoxyorthosilicate (Stober method) were dispersed in a solution of Neodimium nitrate (kept in an ice bath) in a proportion of 98.5 mol% SiO; and 1.5 mol% Nd,O; under sonication followed by the addition of aqueous ammonia by known process. The resulting product was washed with water followed by centrifugation and drying under vacuum. eo A stable dispersion of composition 94.8Si0;: 3GeO, : 2AL03: 0.20 Nd,O; (in equivalent oxide mol%) was prepared for the application of coating to the inner wall of high purity clear fused silica glass tubes. e From the Neodimium oxide (Nd;03) coated silica powders with 98.5 mol% SiO, and 1.5 mol% Nd,Os, a silica sol of composition of 94.8 equivalent mol% of SiO; and 0.20 ‘ equivalent mol% of Nd,O; was prepared by diluting with a slica sol containing the desired amount of silicon tetraethoxide (TEOS). e Silica-germania sol containing 3 equivalent oxide mol% of germanium ethoxide [Ge(OC:Hs)s] was prepared through the hydrolysis of TEOS and [Ge(OC,Hs)s) with n © WO 03/033423 PCT/IN01/00184 water and hydrochloric acid in presence of a mixed solvent of propan-1-ol and butan- 2-ol. pH of the above sol was 1.2 £0.05 . \ e 2 equivalent oxide mol% of [AI(NO;);.9H,0] and 0.20 equivalent mol% of Nd,O3 through Nd,Os coated SiO, powders (after baking at 100°C for 5h) were dispersed in : 5 the above silica sol under sonication (26 kHz) for 80 mins. o The resultant dispersion after allowing to settle for 2 h, was used to coat the inner wall of the throughly cleaned silica glass tubes with inner diameter of 17.9 mm. The outer wall of the tubes were properely masked with a suitable substance (parafilm). e Coating was performed by dipping the silica glass tubes with a speed of 6 cm/min into the dispersion and lifting the same tube from the above dispersions with the same speed. e The coated tubes were dried in air at 80°C for 1.5 h. e Oxidation at temperatures of 700° 820° and 910°C with 2 passes of the burner at each temperature maintaining a constant He/O, ratio of 1:6 . eo The dehydration was carried out at a temperature of 900°C with a Cl,: O, ratio of 2.5 : 1 for a period of 1.25 hour. » For sintering the temperature was increased in 4 steps up to 1225°C, each step consisting of 2 passes of the burner. GeCl, was added in controlled quantities during this stage with the input oxygen with two passes at 1225°C and one pass at 1400°C in order to adjust the NA of the preform / fibre. eo The tube was further heated to increase the temperature stepwise to 1600°C for complete sintering of the Ge, Nd & Al containing coated layer. During sintering O, and
He flow was in the ratio of of 4:1. o The collapsing was done in 3 steps in the usual manner with positive oxygen pressure of 4 psi inside the tube to avoid any deformation in shape or geometry and excessive j evaporation of GeO, or other oxides from the core. eo Overcladding was done to reduce the core:clad ratio to 3.5:125. The NA measured in the fibre was 0.22 + 0.01 . e The Nd* ion concentration in the fibre was 2350 ppm approx.as measured from the absorption at selected wavelengths.
EXAMPLE 3
Eu-doped fibre * Amorphous silica microspheres synthesized by hydrolysis of tetraethoxyorthosilicate (Stober method) were dispersed in a solution of europium nitrate (kept in an ice bath) in a proportion of 99.0 mol% SiO; and 1.0 mol% Eu,03 under sonication followed by the addition of aqueous ammonia by known process. The resulting product was washed with water followed by centrifugation and drying under vacuum. * A stable dispersion of composition 95.99S5i0,: 3GeO, : 1ALO;: 0.01 Eu,0; (in equivalent oxide mol%) was prepared for the application of coating to the inner wall of high purity clear fused silica glass tubes. ¢ From the europium oxide (Eu;0;) coated silica powders with 99.0 mol% SiO, and 1.0 mol% Eu,0s, a silica sol of composition of 95.99 equivalent mol% of SiO, and 0.01 equivalent mol% of Eu;0; was prepared by diluting with a slica sol containing the desired amount of silicon tetraethoxide (TEOS). ¢ Silica-germania sol containing 3 equivalent oxide mol% of germanium ethoxide [Ge(OC;Hs)4] was prepared through the hydrolysis of TEOS and [Ge(OC;Hs)4) with water and hydrochloric acid in presence of a mixed solvent of propan-1-ol and butan- 2-ol. pH of the above sol was 1.0 + 0.05 . eo 1 equivalent oxide mol% of [AI(NOs);.9H,0] and 0.01 equivalent mol% of EuyO; through EuyO; coated SiO, powders (after baking at 100°C for 1h) were dispersed in the above silica sol under sonication (26 kHz) for 80 mins. e The resultant dispersion after allowing to settle for 2 h, was used to coat the inner wall of the throughly cleaned silica glass tubes with inner diameter of 17.8 mm. The outer wall of the tubes were properely masked with a suitable substance (parafilm). o Coating was performed by dipping the silica glass tubes with a speed of 10 cm/min into the dispersion and lifting the same tube from the above dispersions with the same speed. e The coated tubes were dried in air at 100°C for 1h. eo Oxidation at temperatures of 610°, 700°, 825° and 950°C with 2 passes of the burner at each temperature maintaining a constant He/O, ratio of 1:5 . e The dehydration was carried out at a temperature of 1000°C with a Cl: O, ratio of 2 : 1 for a period of one hour.
0 WO 03/033423 . PCT/INO1/00184 e For sintering the temperature was increased in 4 steps up to 1220°C, each step consisting of 2 passes of the burner. GeCl, was added in controlled quantities during this stage with the input oxygen with two passes at 1220°C in order to adjust the NA of the preform / fibre. : 5 eo The tube was further heated to increase the temperature stepwise to 1600°C for complete sintering of the Ge, Eu & Al containing coated layer. During sintering O, and
He flow was in the ratio of of 4:1. e The collapsing was done in 3 steps in the usual manner with positive oxygen pressure of 4 psi inside the tube to avoid any deformation in shape or geometry and excessive evaporation of GeO, or other oxides from the core. ¢ The core:clad ratio before overcladding was 7.2:125. The NA measured in the fibre was 0.14£001. e The presence of Eu in the core was established from the characteristic fluoresence at 624 nm in the preform sample when excited at 392 nm. eo Spectral attenuation was measured in the fibre from 400 nm to 800 nm.
EXAMPLE 4
Tb-doped fibre e Amorphous silica microspheres synthesized by hydrolysis of tetraethoxyorthosilicate (Stober method) were dispersed in a solution of terbium nitrate (kept in an ice bath) in a proportion of 98.5 mol% SiO; and 1.5 mol% Tb;053 under sonication followed by the addition of aqueous ammonia by known process. The resulting product was washed with water followed by centrifugation and drying under vacuum. ¢ A stable dispersion of composition 95.9S10;: 2GeO; : 2A1,03: 0.1 Tb,03 (in equivalent oxide mol%) was prepared for the application of coating to the inner wall of high purity clear fused silica glass tubes. o From the terbium oxide (Tb,03) coated silica powders with 98.5 mol% SiO; and 1.5 mol% Tb;03, a silica sol of composition of 95.9 equivalent mol% of SiO; and 0.1 : equivalent mol% of Tb,O3; was prepared by diluting with a slica sol containing the desired amount of silicon tetraethoxide (TEOS). e Silica-germania sol containing 2 equivalent oxide mol% of germanium ethoxide [Ge(OC;Hs)4] was prepared through the hydrolysis of TEOS and [Ge(OC,Hs)s] with water and hydrochloric acid in presence of a mixed solvent of propan-1-ol and butan-
2-ol. pH of the above sol was 1.2 + 0.05 . e 2 equivalent oxide mol% of [AI(NO;);.9H,0] and 0.1 equivalent mol% of Tb,0; through Tb,0; coated SiO; powders (after baking at 100°C for 1h) were dispersed in the above silica sol under sonication (26 kHz) for 80 mins. eo The resultant dispersion after allowing to settle for 2 h, was used to coat the inner wall of the throughly cleaned silica glass tubes with inner diameter of 20.1 mm. The outer wall of the tubes were properely masked with a suitable substance (parafilm). e Coating was performed by dipping the silica glass tubes with a speed of 10 cm/min into the dispersion and lifting the same tube from the above dispersions with the same speed. e The coated tubes were dried in air at 150°C for 0.5h. e Oxidation at temperatures of 720°, 825° and 950°C with 2 passes of the burner at each temperature maintaining a constant He/O, ratio of 1:6 . e The dehydration was carried out at a temperature of 950°C with a Cl,: O, ratio of 2.5 : 1 for a period of one hour. » For sintering the temperature was increased in 3 steps up to 1200°C, each step consisting of 2 passes of the burner. GeCl, was added in controlled quantities with the input oxygen during the passes at 1200°C in order to adjust the NA of the preform / fibre. : e The tube was further heated to increase the temperature stepwise to 1650°C for complete sintering of the Ge, Tb & Al containing coated layer. During sintering O, and
He flow was in the ratio of of 4:1. e The collapsing was done in 4 steps in the usual manner with positive oxygen pressure of 4 psi inside the tube to avoid any deformation in shape or geometry and excessive evaporation of GeO, or other oxides from the core. e Overcladding was done to reduce the core:clad ratio to 5:125. The NA measured in the fibre was 0.11 £0.01 . e The preform sample was excited at 355 nm and 400 nm and characteristic fluoresence of Tb was measured at 533 nm and 580 nm. e Spectral attenuation was measured in the fibre from 400 nm to 800 nm
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Comparison of the characteristics of RE-doped fibre.fabricated at CGCRI using RE- coated silica nano particles w.r.t. commercially available fibres for special applications
Commercial fibre CGCRI fibre
Clad composition SiO, or SiO, - P,0, -F
Core composition SiO, +GeO, +ALO, + Er,O, [Same (+P,0;) 0.15 - 0.30 0.10 - 0.30
Cut-off wavelength 850 - 1450 nm 850 - 1450 nm 50 - 2000 ppm 50 - 4000 ppm
Fire diameter [1252 1 pm 2521 pm 245 pn (nomina)
Mode Field Diameter 35-80 um 3.0-8.0 um
The main advantages of the present invention are : 1. It provides a process of fabricating RE doped preforms and optical fibres by using RE coated silica nanoparticles as precursors. The RE (Er, Nd, Eu etc.) coated silica nanoparticles are prepared by sonochemical method. 2. The deposition of a porous soot layer at high temperature (1000°C or above) by CVD process inside a fused silica glass tube or on a seed rod (VAD or OVD apparatus) is eliminated for formation of the core. Instead a thin silica gel coating containing other dopants in desired proportions is applied through a silica sol at ambient temperature. 3. The method described in 2 above ensures a better control of the characteristics of the coated layer like porosity, thickness etc. and uniformity along the length of the tube. 4. The difficulties and uncertainties involved in incorporation of the rare-earth ions in desired concentration into the porous soot layer by the solution-doping technique and such other methods are eliminated. 5. The rare-earth oxide coated silica nanoparticles are dispersed at ambient temperature in the silica sol mentioned above under sonication thereby eliminating the possibility of formation of the microcrystallites and clusters of rare-earth ions as in the conventional techniques. 6. The possibility of evaporation of RE salts at high temperatures is considerably eliminated due to the direct addition of RE oxides which prevents change in composition including variation of RE concentration in the core and also reduces the possibility of formation of RE dip at the core centre.
7. The process ensures better control of RE concentration in the doped region and homogeneous distribution of RE ions along the radial direction as well as throughout the length of the preform.
8. The RE incorporation efficiency is much higher compared to the conventional techniques due to direct addition of the RE oxides in to the dispersion.
9. The numerical aperture of the fibre is varied from 0.10 to 0.30 maintaining RE concentration in the core between 50 to 4000 ppm to produce fibres suitable for application as amplifiers, fibre lasers and sensors or different purposes.
10. The addition of Ge(OET), at ambient temperature in the silica sol above reduces the quantity of GeCly which is required at high temperature to achieve the desired NA.
11. The time period of processing the silica tube at high temperature and the number of steps involved for doping of RE ions by the conventional techniques for fabrication of the preform are considerably reduced.
12. The processing of the tube at ambient temperature before sintering and collapsing instead of high temperature involved in the CVD process makes the process less sensitive to the process parameters unlike the conventional processes.
13. The advantages described above increases the reproducibilty and reliability of the process to a great extent.
14. The requirement of precision equipments for control of porous soot deposition, RE incorporation etc. during fabrication of the preform is considerably eliminated which will reduce the capital investment and cost of the product.
15. All the above advantages combined make the process simple and more economic than the conventional processes.
Claims (41)
1. "A process for making rare earth doped optical fibre comprising: using stable dispersions of rare earth (RE) coated silica nanoparticles to obtain silica sol; and applying a thin coating of said silica sol containing suitable dopants selected from a group consisting of Ge, Al and P.
2. A process for making rare earth doped optical fibre, said process comprising: (a) obtaining rare earth (RE) oxide doped silica nanoparticles by sonochemical method; (b) preparing stable dispersions of the silica nanoparticles containing powders in presence of dopants in a silica sol of Si(OC;Hs), under sonication; (c) applying a thin coating of silica sol on an inner surface of high purity clear fused silica glass tubes by sol-gel dip coating technique; (d) drying the coated layer in air at 70° to 150°C; . (e) mounting the tube on glass working lathe for processing by MCVD technique; (f) dehydrating the coated layer inside the tube at a temperature in the range of 800- 1200°C in presence of excess Cl; (g) sintering the coated layer in presence of a mixture of oxygen and helium in the temperature range of 1400 to1750°C for formation of a core; (h) heating the tube gradually up to a temperature of 1900°C for further consolidation of the sintered layer; (1) collapsing the tube by usual method at a temperature in the range of 2000-2300°C to obtain a preform; (J) overcladding the preform with silica tube, and (k) drawing fibres of standard dimensions from the preform by the conventional methods.
3. A process as claimed in claim 2 wherein, the RE oxide is selected from Eu;03, Nd,0s, Tb,05 and Er,05. AMENDED SHEET 21.07.2005
4. A process as claimed in claim 2 wherein, P,0s, and F doped synthetic cladding is deposited within a silica glass substrate tube prior to development of the coating to obtain matched or depressed clad type structure in the preform.
5. A process as claimed in claim 1 wherein, a particle size of the RE coated silica ranges from 50 to 200 nm.
6. A process as claimed in claim 1 wherein, the composition in oxide mol% of SiO: Re,0; in RE coated silica varies from 99.5: 0.5 to 95 : 5.
7. A process as claimed in claim 1 wherein, the equivalent oxide mol% of SiO, in the dispersion varies from 98.5 to 90.5.
8. A process as claimed in claim 1 wherein, a silica sol prepared with Si(OC,Hs)s was used as the diluent of the RE coated silica nanoparticles.
9. A process as claimed in claim 1 wherein, the equivalent oxide mol% of an oxide of said Ge in the dispersion varies from 1.0 to 5.0.
10. A process as claimed in claim 1 wherein, Ge** was added using Ge(OC;Hs)4 in the silica sol.
11. A process as claimed in claim 1 wherein, the equivalent oxide mol% of an oxide of said Al in the dispersion ranges from 0.5 to 4.0.
12. A process as claimed in claim 1 wherein, A1,0; is provided to the solvent in the form of aluminium salts.
13. A process as claimed in claim 1 wherein, a solution of a salt of said Al is prepared using a solvent selected from alcohol and water. AMENDED SHEET 21.07.2005
14. A process as claimed in claim 3 wherein, the oxide mol% of Er;0; in the dispersion ranges from 0.01 to 0.60.
15. A process as claimed in claim 1 wherein, hydrochloric or nitric acid is used for preparing the sol for dispersion.
16. A process as claimed in claim 13 wherein, the alcohol selected is soluable in the dispersion system.
17. A process as claimed in claim 16 wherein, the alcohol is selected from the group consisting of methyl alcohol, ethyl alcohol, propan-1-ol, propan-2-ol, butanol and butan-2-ol.
18. A process as claimed in claim 1 wherein, pH of the dispersion ranges from 1 to 5.
19. A process as claimed in claim 1 wherein, viscosity of the dispersion varies from 1 to mPa s.
20. A process as claimed in claim 1 wherein, a sonication time of the dispersion ranges from 30 to 200 minutes.
21. A process as claimed in claim 1 wherein, a settling time of the dispersion varies from 1 to 10 hours.
22. A process as claimed in claim 2 wherein, a lifting speed of the tube from the dispersion ranges from 4 to 15 cm/minutes.
23. A process as claimed in claim 2 wherein, a baking temperature of the coated tube varies from70° to 150°C. AMENDED SHEET 21.07.2005
24. A process as claimed in claim 2 wherein, a baking time of the coated tube ranges ; from 0.5 to 5 hours.
25. A process as claimed in claim 2 wherein, the core composition is selected from the group consisting of RE;0;. +Si0,+GeO,;, RE;0; +Si0,+GeO, +Al1,0;, RE;0; +S10,+GeO, +AL0; +P,05 and RE,0; +S10,+GeO, + P,0s.
26. A process as claimed in claim 2 wherein, a temperature of the RE oxide containing core layer is increased in steps of 50 t0200 C during the sintering depending on a composition and AI/RE concentration of the core.
27.-A process as claimed in claim 2 wherein, the mixture of 0; and He is in the range of 3:1 to 9:1 during sintering.
28. A process as claimed in claim 2 wherein, source of chlorine is CCl; where helium is used as carrier gas.
29. A process as claimed in claim 2 wherein, a proportion of C1,: 0, during drying varies from1.5:1t03.5:1
30. A process as claimed in claim 2 wherein, a dehydration period lies between 1 to 2 hours.
31. A process as claimed in claim 2 wherein, the core is sintered in the presence of germania .
32. A process as claimed in claim 2 wherein, germania is supplied to the core during sintering by including GeCl, with the oxygen. AMENDED SHEET 21.07.2005
)
33. A process as claimed in claim 2 wherein, the sintering is carried out at a temperature of 1200°C to 1400°C.
34. A process as claimed in claim 2 wherein, POC1; is added to the input gas mixture during sintering.
35. A process as claimed in claim 2 wherein, the core is doped with P,0s.
36. A process as claimed in claim 2 wherein, P,0s and GeO, concentrations vary from 0.5 to 5.0 mol% and 3.0 to 25.0 mol% respectively in the RE doped core.
37. A process as claimed in claim 2 wherein, the numerical aperture of the fibre is varied from 0.10 to 0.30.
38. A process as claimed in claim 2 wherein, RE concentration in the core is maintained in the range of 50 to 4000 ppm.
39. A process as claimed in claim 2 wherein, codopants are added to the core in the concentration range 50 to 5000 ppm and numerical aperture varying between 0.10 and 0.30.
40. A process as claimed in claim 1 wherein, the rare-earth oxide coated silica nanoparticles are dispersed at ambient temperature in the silica sol under sonication.
41. A process for making rare earth doped optical fibre comprising using stable dispersions of rare earth (RE) coated silica nanoparticles to obtain silica sol, substantially as herein described with reference to any of the illustrative Examples 1 to 4. AMENDED SHEET 21.07.2005
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA200403772A ZA200403772B (en) | 2004-05-17 | 2004-05-17 | A process of making rare earth doped optical fibre. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA200403772A ZA200403772B (en) | 2004-05-17 | 2004-05-17 | A process of making rare earth doped optical fibre. |
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| Publication Number | Publication Date |
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| ZA200403772B true ZA200403772B (en) | 2005-07-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| ZA200403772A ZA200403772B (en) | 2004-05-17 | 2004-05-17 | A process of making rare earth doped optical fibre. |
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| Country | Link |
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| ZA (1) | ZA200403772B (en) |
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2004
- 2004-05-17 ZA ZA200403772A patent/ZA200403772B/en unknown
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