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Optical Materials Express

Optical Materials Express

  • Editor: David J. Hagan
  • Vol. 2, Iss. 10 — Oct. 1, 2012
  • pp: 1391–1396
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Phosphorous doping and drawing effects on the Raman spectroscopic properties of O = P bond in silica-based fiber and preform

A. Alessi, S. Girard, M. Cannas, A. Boukenter, and Y. Ouerdane  »View Author Affiliations


Optical Materials Express, Vol. 2, Issue 10, pp. 1391-1396 (2012)
http://dx.doi.org/10.1364/OME.2.001391


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Abstract

We report an experimental study of the doping and drawing effects on the Raman activities of phosphorus (P)-doped silica-based optical fiber and its related preform. Our data reveal a high sensitivity level in the full width at half maximum value of the 1330 cm−1 (O = P) Raman band to the P-doping level. Its increase with the P doping level does not clash with an increase in the disorder of the O = P surrendering matrix. In addition, we observe that in the central core region of the sample (higher doping level), the drawing process decreases the relative band amplitude. We tentatively suggest that this phenomenon is due to the change in the first derivate of the bond polarizability as a function of the normal vibration coordinates.

© 2012 OSA

1. Introduction

The present investigation highlights the drawing effects on P-doped silica-based glasses structure to provide evidence for the changes induced by this process. In this study, we recorded confocal micro-Raman spectra on both fiber and its original preform. Thanks to the particular structure of the prototype investigated sample, we also investigated the effects of the P-doping levels on the spectroscopic features of the O = P Raman band.

2. Experimental

The investigated fiber, named FP, was manufactured by iXFiber S.A.S starting with a preform (named PP) produced by the modified chemical vapor deposition process (MCVD). The fiber was produced using drawing tension and speed of 60 g and 40m/min respectively.

The doping profiles of the samples are illustrated in Fig. 1
Fig. 1 Radial distribution of P content in the FP (-●-) and in the PP (▬) samples along the fiber and preform diameters. The data for the preform were re-scaled by a factor of 103 that corresponds to the ratio between the preform and the fiber diameters. The P content in the fiber was estimated with an error of 5%.
. They consist of five concentric cylindrical layers with different P-doping contents ranging from virtually absent in the pure silica cladding to a maximum of ~7 weight % in the central part of the core. The fiber doping profile reported in Fig. 1 was obtained by electron microprobe analysis, whereas the doping profile of the preform is designed during the layers deposition phase.

We recorded confocal micro-Raman spectra along the sample diameters using an Aramis (Jobin-Yvon) spectrometer. This setup is supplied by a CCD camera, a He–Cd ion laser (energy 3.8 eV and power ~0.15 mW), a step motor and by 40x objectives. The spectra were acquired, at room temperature, with experimental conditions ensuring a spatial resolution of ~5 μm.

3. Results

3.1 Raman spectra of the preform

3.2 Fiber and preform comparison

Figure 4a
Fig. 4 Raman spectra recorded in the fiber (▬) and in the preform (▬). Panel a: core region doped with 7.4 wt % of P; level. Panel b: 4.8 wt% P-doped region.
compares the Raman spectra recorded in the central cores of the fiber and of the preform.

4. Discussion

The two other possibilities that could explain this change are a decrease in the O = P bond concentration and the modification of its scattering properties. To understand if O = P bonds are destroyed, we have to consider the investigation presented in [14

14. V. G. Plotnichenko, V. O. Sokolov, V. V. Koltashev, V. B. Sulimov, and E. M. Dianov, “UV-irradiation-induced structural transformation in phosphosilicate glass fiber,” Opt. Lett. 23(18), 1447–1449 (1998). [CrossRef] [PubMed]

] where it was suggested that the transformation O = P(O-Si)3→P(O-Si)5 has an energy barrier of ~0.3 eV, whereas the inverse one has an energy barrier of ~0.7 eV. This transformation should be accompanied by the decrease in the Raman signal at about 1150, 680 and 530 cm−1 and by the increase of the Raman signal at about 1060 and 890 cm−1. Since our measurement provides no evidence of any negative component in the difference between the spectra of the fiber and of the preform (see Fig. 5b) we can exclude this possibility. Furthermore, it is also assumed that O = P are not destroyed and transformed in the paramagnetic O-P (r-POHC [8

8. G. Origlio, F. Messina, S. Girard, M. Cannas, A. Boukenter, and Y. Ouerdane, “Spectroscopic studies of the origin of radiation-induced degradation in phosphorus-doped optical fibers and preforms,” J. Appl. Phys. 108(12), 123103 (2010). [CrossRef]

] or l-POCH [8

8. G. Origlio, F. Messina, S. Girard, M. Cannas, A. Boukenter, and Y. Ouerdane, “Spectroscopic studies of the origin of radiation-induced degradation in phosphorus-doped optical fibers and preforms,” J. Appl. Phys. 108(12), 123103 (2010). [CrossRef]

]). This assumption is supported by the following considerations. In the core, about 3 1021 P atoms/cm3 are present and most of them are involved in O = P linkages [9

9. V. G. Plotnichenko, V. O. Sokolov, V. V. Koltashev, and E. M. Dianov, “On the structure of phosphosilicate glasses,” J. Non-Cryst. Solids 306(3), 209–226 (2002). [CrossRef]

], so that a 20% of decrease in the 1330 cm−1 amplitude should induce the formation of several 1020 defects/cm3 whereas in [8

8. G. Origlio, F. Messina, S. Girard, M. Cannas, A. Boukenter, and Y. Ouerdane, “Spectroscopic studies of the origin of radiation-induced degradation in phosphorus-doped optical fibers and preforms,” J. Appl. Phys. 108(12), 123103 (2010). [CrossRef]

] with electron paramagnetic resonance (EPR) measurements we did not observe the presence of detectable signal before any irradiation. Since the stable POHC [13

13. M. Fanciulli, E. Bonera, S. Nokhrin, and G. Pacchioni, “Phosphorous–oxygen hole centers in phosphosilicate glass films,” Phys. Rev. B 74(13), 134102 (2006). [CrossRef]

,15

15. D. L. Griscom, E. J. Friebele, K. J. Long, and J. W. Fleming, “Fundamental defect centers in glass: Electron spin resonance and optical absorption studies of irradiated phosphorus-doped silica glass and optical fibers,” J. Appl. Phys. 54(7), 3743–3762 (1983). [CrossRef]

] (r-POHC) have the [(O-)2P( = O)2] as more probable precursors [13

13. M. Fanciulli, E. Bonera, S. Nokhrin, and G. Pacchioni, “Phosphorous–oxygen hole centers in phosphosilicate glass films,” Phys. Rev. B 74(13), 134102 (2006). [CrossRef]

,15

15. D. L. Griscom, E. J. Friebele, K. J. Long, and J. W. Fleming, “Fundamental defect centers in glass: Electron spin resonance and optical absorption studies of irradiated phosphorus-doped silica glass and optical fibers,” J. Appl. Phys. 54(7), 3743–3762 (1983). [CrossRef]

], whereas the room temperature not stable POHC [13

13. M. Fanciulli, E. Bonera, S. Nokhrin, and G. Pacchioni, “Phosphorous–oxygen hole centers in phosphosilicate glass films,” Phys. Rev. B 74(13), 134102 (2006). [CrossRef]

,15

15. D. L. Griscom, E. J. Friebele, K. J. Long, and J. W. Fleming, “Fundamental defect centers in glass: Electron spin resonance and optical absorption studies of irradiated phosphorus-doped silica glass and optical fibers,” J. Appl. Phys. 54(7), 3743–3762 (1983). [CrossRef]

] (l-POHC) have the [(O-)3P = O] as more probable precursors [13

13. M. Fanciulli, E. Bonera, S. Nokhrin, and G. Pacchioni, “Phosphorous–oxygen hole centers in phosphosilicate glass films,” Phys. Rev. B 74(13), 134102 (2006). [CrossRef]

,15

15. D. L. Griscom, E. J. Friebele, K. J. Long, and J. W. Fleming, “Fundamental defect centers in glass: Electron spin resonance and optical absorption studies of irradiated phosphorus-doped silica glass and optical fibers,” J. Appl. Phys. 54(7), 3743–3762 (1983). [CrossRef]

], one could speculate that the decrease in the Raman band is due to the generation of the second types of POHC. To exclude this hypothesis, we also have to consider the following data previously reported in ref [8

8. G. Origlio, F. Messina, S. Girard, M. Cannas, A. Boukenter, and Y. Ouerdane, “Spectroscopic studies of the origin of radiation-induced degradation in phosphorus-doped optical fibers and preforms,” J. Appl. Phys. 108(12), 123103 (2010). [CrossRef]

]. The l-POHC defects were observed at room temperature in the EPR spectra of the preform. In ref [13

13. M. Fanciulli, E. Bonera, S. Nokhrin, and G. Pacchioni, “Phosphorous–oxygen hole centers in phosphosilicate glass films,” Phys. Rev. B 74(13), 134102 (2006). [CrossRef]

], based on their calculation, the authors do not rule out that a l-POHC (metastable) can become a r-POHC (stable) after an internal conversion involving the braking of a near Si-O bond.

5. Conclusion

We have investigated the Raman activity of a 4- steps P doped fiber and its original preform. Our data indicate that the FWHM of the Raman band of the O = P bond increases with the P content. This result may suggest larger distributions of the structural parameters of the O = P bond or of its surrounding matrix which affect its Raman activity. Furthermore, we observe significant change in the Raman spectra after the drawing only in the highly P-doped central zone. Such variation concerns the relative amplitude of the O = P component. After excluding various possible reasons, we tentatively suggest that the first derivate of the polarizability as a function of the normal vibration coordinates is changed because of structure modifications. Further investigations will be performed to confirm this hypothesis as well as to clarify the fact that this effect is observed only in the central part of the core. Anyway, our data provide evidence for the drawing effects on the P doped silica structure, which have to be taken into account for fiber production.

Acknowledgments

We acknowledge the members of the LAMP group (http://www.fisica.unipa.it/amorphous/) for support with interesting discussions.

References and links

1.

G. Pacchioni, L. Skuja, and D. L. Griscom, eds., Defects in SiO2 and Related Dielectrics: Science and Technology (Kluwer Academic, Dordrecht, 2000).

2.

R. Kitamura, L. Pilon, and M. Jonasz, “Optical constants of silica glass from extreme ultraviolet to far infrared at near room temperature,” Appl. Opt. 46(33), 8118–8133 (2007). [CrossRef] [PubMed]

3.

A. J. Ikushima, T. Fujiwara, and K. Saito, “Silica glass: A material for photonics,” J. Appl. Phys. 88(3), 1201–1213 (2000). [CrossRef]

4.

R. A. B. Devine, J. P. Duraud, and E. Dooryhée, eds., Structure and Imperfections in Amorphous and Crystalline Silicon Dioxide (John Wiley & Sons, LTD, New York, 2000).

5.

D. Ehrt, P. Ebeling, and U. Natura, “UV Transmission and radiation-induced defects in phosphate and fluoride-phosphate glasses,” J. Non-Cryst. Solids 263-264, 240–250 (2000). [CrossRef]

6.

P. L. Kelly, I. Kaminov, and G. Agrawal, eds., Erbium-Doped Fiber Amplifiers, Fundamental and Technology (Academic, London, 1999).

7.

E. M. Dianov, M. V. Grekov, I. A. Bufetov, S. A. Vasiliev, O. I. Medvedkov, V. G. Plotnichenko, V. V. Koltashev, A. V. Belov, M. M. Bubnov, S. L. Semjonov, and A. M. Prokhorov, “CW high power 1.24 μm and 1.48 μm Raman lasers based on low loss phosphosilicate fibre,” Electron. Lett. 33(18), 1542–1544 (1997). [CrossRef]

8.

G. Origlio, F. Messina, S. Girard, M. Cannas, A. Boukenter, and Y. Ouerdane, “Spectroscopic studies of the origin of radiation-induced degradation in phosphorus-doped optical fibers and preforms,” J. Appl. Phys. 108(12), 123103 (2010). [CrossRef]

9.

V. G. Plotnichenko, V. O. Sokolov, V. V. Koltashev, and E. M. Dianov, “On the structure of phosphosilicate glasses,” J. Non-Cryst. Solids 306(3), 209–226 (2002). [CrossRef]

10.

N. Shibata, M. Horigudhi, and T. Edahiro, “Raman spectra of binary high-silica glasses and fibers containing GeO2, P2O5 and B2O3,” J. Non-Cryst. Solids 45(1), 115–126 (1981). [CrossRef]

11.

F. L. Galeener and A. E. Geissberger, “Vibrational dynamics in 30Si-substituted vitreous SiO2,” Phys. Rev. B 27(10), 6199–6204 (1983). [CrossRef]

12.

F. L. Galeener and G. Lucovsky, “Longitudinal optical vibrations in glasses: GeO2 and SiO2,” Phys. Rev. Lett. 37(22), 1474–1478 (1976). [CrossRef]

13.

M. Fanciulli, E. Bonera, S. Nokhrin, and G. Pacchioni, “Phosphorous–oxygen hole centers in phosphosilicate glass films,” Phys. Rev. B 74(13), 134102 (2006). [CrossRef]

14.

V. G. Plotnichenko, V. O. Sokolov, V. V. Koltashev, V. B. Sulimov, and E. M. Dianov, “UV-irradiation-induced structural transformation in phosphosilicate glass fiber,” Opt. Lett. 23(18), 1447–1449 (1998). [CrossRef] [PubMed]

15.

D. L. Griscom, E. J. Friebele, K. J. Long, and J. W. Fleming, “Fundamental defect centers in glass: Electron spin resonance and optical absorption studies of irradiated phosphorus-doped silica glass and optical fibers,” J. Appl. Phys. 54(7), 3743–3762 (1983). [CrossRef]

16.

E. M. Dianov, V. V. Koltashev, P. G. Plotnichenko, V. O. Sokolov, and V. B. Sulimov, “UV irradiation-induced structural transformation in phosphosilicate glass,” J. Non-Cryst. Solids 249(1), 29–40 (1999). [CrossRef]

OCIS Codes
(060.2280) Fiber optics and optical communications : Fiber design and fabrication
(060.2290) Fiber optics and optical communications : Fiber materials
(060.2310) Fiber optics and optical communications : Fiber optics
(160.2750) Materials : Glass and other amorphous materials
(300.6450) Spectroscopy : Spectroscopy, Raman

ToC Category:
Materials for Fiber Optics

History
Original Manuscript: June 8, 2012
Revised Manuscript: July 28, 2012
Manuscript Accepted: July 28, 2012
Published: September 14, 2012

Citation
A. Alessi, S. Girard, M. Cannas, A. Boukenter, and Y. Ouerdane, "Phosphorous doping and drawing effects on the Raman spectroscopic properties of O = P bond in silica-based fiber and preform," Opt. Mater. Express 2, 1391-1396 (2012)
http://www.opticsinfobase.org/ome/abstract.cfm?URI=ome-2-10-1391


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References

  1. G. Pacchioni, L. Skuja, and D. L. Griscom, eds., Defects in SiO2 and Related Dielectrics: Science and Technology (Kluwer Academic, Dordrecht, 2000).
  2. R. Kitamura, L. Pilon, and M. Jonasz, “Optical constants of silica glass from extreme ultraviolet to far infrared at near room temperature,” Appl. Opt.46(33), 8118–8133 (2007). [CrossRef] [PubMed]
  3. A. J. Ikushima, T. Fujiwara, and K. Saito, “Silica glass: A material for photonics,” J. Appl. Phys.88(3), 1201–1213 (2000). [CrossRef]
  4. R. A. B. Devine, J. P. Duraud, and E. Dooryhée, eds., Structure and Imperfections in Amorphous and Crystalline Silicon Dioxide (John Wiley & Sons, LTD, New York, 2000).
  5. D. Ehrt, P. Ebeling, and U. Natura, “UV Transmission and radiation-induced defects in phosphate and fluoride-phosphate glasses,” J. Non-Cryst. Solids263-264, 240–250 (2000). [CrossRef]
  6. P. L. Kelly, I. Kaminov, and G. Agrawal, eds., Erbium-Doped Fiber Amplifiers, Fundamental and Technology (Academic, London, 1999).
  7. E. M. Dianov, M. V. Grekov, I. A. Bufetov, S. A. Vasiliev, O. I. Medvedkov, V. G. Plotnichenko, V. V. Koltashev, A. V. Belov, M. M. Bubnov, S. L. Semjonov, and A. M. Prokhorov, “CW high power 1.24 μm and 1.48 μm Raman lasers based on low loss phosphosilicate fibre,” Electron. Lett.33(18), 1542–1544 (1997). [CrossRef]
  8. G. Origlio, F. Messina, S. Girard, M. Cannas, A. Boukenter, and Y. Ouerdane, “Spectroscopic studies of the origin of radiation-induced degradation in phosphorus-doped optical fibers and preforms,” J. Appl. Phys.108(12), 123103 (2010). [CrossRef]
  9. V. G. Plotnichenko, V. O. Sokolov, V. V. Koltashev, and E. M. Dianov, “On the structure of phosphosilicate glasses,” J. Non-Cryst. Solids306(3), 209–226 (2002). [CrossRef]
  10. N. Shibata, M. Horigudhi, and T. Edahiro, “Raman spectra of binary high-silica glasses and fibers containing GeO2, P2O5 and B2O3,” J. Non-Cryst. Solids45(1), 115–126 (1981). [CrossRef]
  11. F. L. Galeener and A. E. Geissberger, “Vibrational dynamics in 30Si-substituted vitreous SiO2,” Phys. Rev. B27(10), 6199–6204 (1983). [CrossRef]
  12. F. L. Galeener and G. Lucovsky, “Longitudinal optical vibrations in glasses: GeO2 and SiO2,” Phys. Rev. Lett.37(22), 1474–1478 (1976). [CrossRef]
  13. M. Fanciulli, E. Bonera, S. Nokhrin, and G. Pacchioni, “Phosphorous–oxygen hole centers in phosphosilicate glass films,” Phys. Rev. B74(13), 134102 (2006). [CrossRef]
  14. V. G. Plotnichenko, V. O. Sokolov, V. V. Koltashev, V. B. Sulimov, and E. M. Dianov, “UV-irradiation-induced structural transformation in phosphosilicate glass fiber,” Opt. Lett.23(18), 1447–1449 (1998). [CrossRef] [PubMed]
  15. D. L. Griscom, E. J. Friebele, K. J. Long, and J. W. Fleming, “Fundamental defect centers in glass: Electron spin resonance and optical absorption studies of irradiated phosphorus-doped silica glass and optical fibers,” J. Appl. Phys.54(7), 3743–3762 (1983). [CrossRef]
  16. E. M. Dianov, V. V. Koltashev, P. G. Plotnichenko, V. O. Sokolov, and V. B. Sulimov, “UV irradiation-induced structural transformation in phosphosilicate glass,” J. Non-Cryst. Solids249(1), 29–40 (1999). [CrossRef]

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