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Optics Express

Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 16, Iss. 9 — Apr. 28, 2008
  • pp: 6502–6506
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Three-photon-excited upconversion luminescence of niobium ions doped silicate glass by a femtosecond laser irradiation

Huidan Zeng, Juan Song, Danping Chen, Shuanglong Yuan, Xiongwei Jiang, Ya Cheng, Yunxia Yang, and Guorong Chen  »View Author Affiliations


Optics Express, Vol. 16, Issue 9, pp. 6502-6506 (2008)
http://dx.doi.org/10.1364/OE.16.006502


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Abstract

We report on the bluish green upconversion luminescence of niobium ions doped silicate glass by a femtosecond laser irradiation. The dependence of the fluorescence intensity on the pump power density of laser indicates that the conversion of infrared irradiation to visible emission is dominated by three-photon excitation process. We suggest that the charge transfer from O2- to Nb5+ can efficiently contribute to the bluish green emission. The results indicate that transition metal ions without d electrons play an important role in fields of optics when embedded into silicate glass matrix.

© 2008 Optical Society of America

1. Introduction

In recent years, femtosecond laser pulses have been widely studied because of its ultra high power density and the corresponding multi-photon reactions. Various microstructures were observed when the femtosecond laser pulse was focused into transparent material. In particular, the space-selective modified structures can be used to fabricate three-dimensional integrated photonic devices such as optical waveguide [1

1. K. M. Davis, K. Miura, N. Sugimoto, and K. Hirao, “Writing waveguides in glass with a femtosecond laser,” Opt. Lett. 21, 1729–31 (1996). [CrossRef] [PubMed]

], photonic crystal [2

2. H. Sun, Y. Xu, S. Matsuo, and H. Misawa, “Microfabrication and characteristics of two-dimensional photonic crystal. structures in vitreous silica,” Opt. Rev. 6, 396–398 (1999). [CrossRef]

], optical memory and so on [3

3. M. Watanabe, S. Juodkazis, H. B. Sun, S. Matsuo, and H. Misawa, “Two-photon readout of three-dimensional memory in silica,” Appl. Phys. Lett. 77, 13–15 (2000). [CrossRef]

, 4

4. C. B. Schaffer, A. Brodeur, J. F. García, and E. Mazur, “Micromachining bulk glass by use of femtosecond laser pulses with nanojoule energy,” Opt. Lett. 26, 93–95 (2001). [CrossRef]

].

Upconversion luminescence has attracted a lot of attention in the past decade. Researchers have investigated rare-earth-ion-doped transparent solid-state materials [5

5. L. F. Johnson and G. J. Guggenheim, “Infrared-Pumped Visible Laser,” Appl. Phys. Lett. 19, 44–47 (1971). [CrossRef]

], in which the predominant mechanisms of the upconversion are energy transfer, excited-state absorption, cooperative upconversion, and photon avalanche. Recently, there have been some reports on upconversion of rare earth ions and transition metal ions due to multi-photon absorption under femtosecond laser irradiation [6-10

6. L. Yang, Y. Dong, D. Chen, C. Wang, X. Hu, N. Da, G. Zhao, J. Xua, X. Jiang, C. Zhu, and J. Qiu, “Three-photon-excited upconversion luminescence of Ce3+: YAP crystal by femtosecond laser irradiation,” Opt. Express 14, 243–247 (2006). [CrossRef] [PubMed]

]. For example, Meng et al reported intense upconversion emission of transition metal ions such as Ti4+ and Ta5+ in oxide glass by femtosecond laser irradiation. In this paper, we report for the first time the upconversion luminescence in Nb5+ ions doped silicate glass, i.e., the observation of intense visible emission under near-infrared femtosecond pulsed laser irradiation. The results indicate that transition-metal ion Nb5+ with vacant d orbitals, exhibits similar upconversion luminescence feature, thus playing a potential role in the field of optical storage, optical display etc.

2. Experiments

Traditional Na2O-CaO-SiO2 silicate glass system was chosen as the host for metal dopant due to its excellent glass-forming ability, higher solubility for noble elements and higher stability. The compositions (in mol %) of tested samples are 20Na2O·10CaO·70SiO2 (Sample 1, matrix) and 20Na2O·10CaO·69SiO2·1Nb2O5 (Sample 2), About 100 g batches were melted in a platinum crucible at temperature 1550 °C for 3 hrs. The resultant colorless and transparent glasses were cut and polished into 1 mm-thick plates.

Light source for irradiating the glass samples was a regeneratively amplified 800 nm, 120 fs, 1 kHz mode-locked Ti: Sapphire laser (Tsunami model 3960c, Spectra Physics). The samples were put on a three-dimensional XYZ stage controlled by a computer. The laser beam was focused by an optical lens with focal length of 100 mm into the glass sample, about 0.5 mm beneath the surface. Upconversion emission spectra were obtained by ZOLIX SBP 300 fluorescence spectrophotometer. Fluorescence spectra were also recorded on JASCO 6500 fluorescence spectrophotometer by using a Xe lamp as an excitation source. The emission and the excitation spectra were recorded using a JASCO FP-6500 fluorescence spectrofluorometer at room temperature. Optical absorption spectral measurements were performed with a JASCO-V570 UV-VIS-NIR spectrophotometer. All the measurements were carried out at room temperature.

3. Results and discussion

The niobium ions doped glass sample can yield a bluish green emission observable even with the naked eye under femtosecond laser irradiation. The spectrum is shown in Fig. 1. The glass sample containing niobium ions (Sample 2) produces a broad band fluorescence from 350 nm to 650 nm peaked at about 480 nm, while glass matrix (Sample 1) does not show obvious emission in this region. The emission spectrum of Sample 2 excited by 267 nm monochromatic light from a xenon lamp is also shown in Fig. 1 for comparison. Although the intensity of upconversion pumped by NIEPL is different from that by UV excitation due to the dissimilar fluorescence measurement condition, their spectral profile is almost the same, indicating that the emissions in both cases come from an identical origin.

Fig. 1. Emission spectra of the niobium ions doped glass sample under focused 800 nm femtosecond laser irradiation and 267 nm monochromatic light excitation, respectively.

The PL around 480 nm found for niobium ions-doped silicate glass, as shown in Fig. 1, has not been reported until now to our knowledge. Though the emission from Sample 1 is invisible, the niobium ions-doped glass sample shows bluish green emission. Since little information is available on the emission from niobium ions in glass hosts, and there is no emission in niobium ions, we thus refer to the luminescence from closed-shell d0 oxo-complexes such as vanadate [13

13. S. H. Shin, D. Y. Jeon, and K. S. Suh, “Charge-transfer nature in luminescence of YNbO4: Bi blue phosphor,” J. Appl. Phys. 90, 5986 (2001). [CrossRef]

], titanium [8

8. X. Meng, K. Tanaka, K. Fujita, and S. Murai, “Intense greenish emission from d0 transition metal ion Ti4+ in oxide glass,” Appl. Phys. Lett. 90, 051917 (2007). [CrossRef]

] and niobium - contained crystal [14

14. G. Blasse and F. van To1, “Luminescence of KNb3O8,” Solid State Comm. 95, 465–468 (1995). [CrossRef]

]. Their optical absorption and emission are usually ascribed to charge transfer transitions between the oxygen 2p orbitals and the empty d orbitals of the transition metal ions.

Fig. 2. Log–log relationship between the emission intensity and the pump power of the femtosecond pulsed laser for Sample 2.

Table 1. Luminescence from closed-shell d0 oxo-complexes

table-icon
View This Table

Figure 3 shows the absorption spectra of Sample 1 (curve a), sample 2 (b), the difference spectrum (c) between Sample 1 and Sample 2, and the excitation spectrum of Sample 2 obtained by monitoring the emission at 480 nm (d). The difference absorption spectrum exhibits a narrow band centered at 280 nm extending from 250 to 300 nm, which may be ascribed to the charge transfer from O2- to Nb5+. The difference of absorption intensity is high, which indicates that this absorption band contributes to bluish green emission efficiently. Indeed, strong bluish green emission excited by UV photons has been observed in the present investigation. The profile of excitation spectrum is well consistent with the difference absorption spectrum shown in Fig. 3 except for a little shift in peak position. No overlap occurs in excitation and emission spectra, which means that the excitation process of Nb–O charge transfer band can efficiently contribute to the bluish green emission.

Fig. 3. Absorption spectra of Sample 1 (a), sample 2 (b), the difference spectrum (c) between Sample 1 and Sample 2, and the excitation spectrum of Sample 2 obtained by monitoring the emission at 480 nm (d).

Based on the above discussion, we propose the following mechanisms for the efficient broad band visible upconversion luminescence. That’s, Nb5+ ions is incorporated into the silicate glass network as distorted MO octahedron, substituting SiO4 groups and giving rise to non-bridging oxygens. In the glass network, Nb5+ ions exist mainly as NbO- 6 octahedron which shares side with SiO4 [16

16. A. Aronne, V. N. Sigaev, B. Champagnon, E. Fanelli, V. Califano, L. Z. Usmanova, and P. Pernice, “The origin of nanostructuring in potassium niobiosilicate glasses by Raman and FTIR spectroscopy,” J. Non-Cryst. Solids 351, 3610–3618 (2005). [CrossRef]

]. The transition involved is a charge transfer from oxygen to the d0 ion. An electron is exited from a non-bonding orbital (on the oxygen ions) to an antibonding orbital (main do on the Nb5+ ions). An electron in the 2p orbital of oxide ions is excited to the Nb5+ 4d0 energy level by absorbing three 800 nm photons. The excited electron thermally relaxes to the lowest vibrational level of Nb5+ 4d0 state; and then radiatively relaxes to the 2p orbital of oxide ions accompanied by emission of a bluish green wavelength photon.

4. Conclusions

In summary, we have experimentally demonstrated upconversion luminescence in niobium ions doped silicate glass by a focused infrared femtosecond laser irradiation. The relationship between the fluorescence intensity and the pump power density shows that the pump process is a three-photon excitation process.

The glass materials presented herein are expected to find applications in high density optical storage, colorless transparent fluorescence material and three-dimensional color displays.

Acknowledgments

The authors wish to thank Prof. X. Zhang (University of Rennes 1, Rennes, France), Dr L. Yang (National Institute of Advanced Industrial Science and Technology (AIST), Osaka, Japan) and Dr. Q. Zhao (Institute of Optics, Information and Photonics, University Erlangen-Nuremberg, Erlangen, Germany) for helpful discussions. The present work is supported by the National Natural Science Foundation of China (50702021), Research Fund for Young Teachers for the Doctoral Program by Ministry of Education of China (No. 20070251013) and Key Laboratory of Silicate Materials Science and Engineering (Wuhan University of Technology), Ministry of Education (No. SYSJJ2007-05).

References and links

1.

K. M. Davis, K. Miura, N. Sugimoto, and K. Hirao, “Writing waveguides in glass with a femtosecond laser,” Opt. Lett. 21, 1729–31 (1996). [CrossRef] [PubMed]

2.

H. Sun, Y. Xu, S. Matsuo, and H. Misawa, “Microfabrication and characteristics of two-dimensional photonic crystal. structures in vitreous silica,” Opt. Rev. 6, 396–398 (1999). [CrossRef]

3.

M. Watanabe, S. Juodkazis, H. B. Sun, S. Matsuo, and H. Misawa, “Two-photon readout of three-dimensional memory in silica,” Appl. Phys. Lett. 77, 13–15 (2000). [CrossRef]

4.

C. B. Schaffer, A. Brodeur, J. F. García, and E. Mazur, “Micromachining bulk glass by use of femtosecond laser pulses with nanojoule energy,” Opt. Lett. 26, 93–95 (2001). [CrossRef]

5.

L. F. Johnson and G. J. Guggenheim, “Infrared-Pumped Visible Laser,” Appl. Phys. Lett. 19, 44–47 (1971). [CrossRef]

6.

L. Yang, Y. Dong, D. Chen, C. Wang, X. Hu, N. Da, G. Zhao, J. Xua, X. Jiang, C. Zhu, and J. Qiu, “Three-photon-excited upconversion luminescence of Ce3+: YAP crystal by femtosecond laser irradiation,” Opt. Express 14, 243–247 (2006). [CrossRef] [PubMed]

7.

L. Yang, Y. Dong, D. Chen, C. Wang, N. Da, X. Jiang, C. Zhu, and J. Qiu, “Upconversion luminescence from 2E state of Cr3+ in Al2O3 crystal by infrared femtosecond laser irradiation,” Opt. Express 13, 7893–98 (2005). [CrossRef] [PubMed]

8.

X. Meng, K. Tanaka, K. Fujita, and S. Murai, “Intense greenish emission from d0 transition metal ion Ti4+ in oxide glass,” Appl. Phys. Lett. 90, 051917 (2007). [CrossRef]

9.

X. Meng, K. Tanaka, S. Murai, K. Fujita, K. Miura, and K. Hirao, “Two-photon-excited fluorescence from silicate glass containing tantalum ions pumped by a near-infrared femtosecond pulsed laser,” Opt. Lett. 31, 2867–69 (2006). [CrossRef] [PubMed]

10.

S. Zhang, B. Zhu, S. Zhou, S. Xu, and J. Qiu, “Multi-photon absorption upconversion luminescence of a Tb3+-doped glass excited by an infrared femtosecond laser,” Opt. Express 15, 6883–88 (2007). [CrossRef] [PubMed]

11.

R. P. Chin, Y. R. Shen, and V. Petrova-koch, “Photoluminescence from porous silicon by infrared multiphoton excitation,” Science 270, 776–778 (1995). [CrossRef]

12.

S. Juodkazis, A. V. Rode, E. G. Gamaly, S. Matsuo, and H. Misawa, “Recording and reading of three-dimensional optical memory in glasses,” Appl. Phys. B: Lasers Opt. 77, 361–368 (2003). [CrossRef]

13.

S. H. Shin, D. Y. Jeon, and K. S. Suh, “Charge-transfer nature in luminescence of YNbO4: Bi blue phosphor,” J. Appl. Phys. 90, 5986 (2001). [CrossRef]

14.

G. Blasse and F. van To1, “Luminescence of KNb3O8,” Solid State Comm. 95, 465–468 (1995). [CrossRef]

15.

D. Chen, L. Yang, M. Peng, C. Wang, N. Da, Y. Qiao, Q. Zhou, C. Zhu, and T. Akai, “Preparation and fluorescent property of Eu-doped high silica glasses,” J. Rare Earths 24, 191–195 (2006). [CrossRef]

16.

A. Aronne, V. N. Sigaev, B. Champagnon, E. Fanelli, V. Califano, L. Z. Usmanova, and P. Pernice, “The origin of nanostructuring in potassium niobiosilicate glasses by Raman and FTIR spectroscopy,” J. Non-Cryst. Solids 351, 3610–3618 (2005). [CrossRef]

OCIS Codes
(140.7090) Lasers and laser optics : Ultrafast lasers
(160.2750) Materials : Glass and other amorphous materials
(190.4180) Nonlinear optics : Multiphoton processes
(190.7220) Nonlinear optics : Upconversion

ToC Category:
Nonlinear Optics

History
Original Manuscript: February 19, 2008
Revised Manuscript: April 15, 2008
Manuscript Accepted: April 15, 2008
Published: April 23, 2008

Citation
Huidan Zeng, Juan Song, Danping Chen, Shuanglong Yuan, Xiongwei Jiang, Ya Cheng, Yunxia Yang, and Guorong Chen, "Three-photon-excited upconversion luminescence of niobium ions doped silicate glass by a femtosecond laser irradiation," Opt. Express 16, 6502-6506 (2008)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-16-9-6502


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References

  1. K. M. Davis, K. Miura, N. Sugimoto, and K. Hirao, "Writing waveguides in glass with a femtosecond laser," Opt. Lett. 21, 1729-31 (1996). [CrossRef] [PubMed]
  2. H. Sun, Y. Xu, S. Matsuo, and H. Misawa, "Microfabrication and characteristics of two-dimensional photonic crystal. structures in vitreous silica," Opt. Rev. 6,396-398 (1999). [CrossRef]
  3. M. Watanabe, S. Juodkazis, H. B. Sun, S. Matsuo, and H. Misawa, "Two-photon readout of three-dimensional memory in silica," Appl. Phys. Lett. 77, 13-15 (2000). [CrossRef]
  4. C. B. Schaffer, A. Brodeur, J. F. García, and E. Mazur, "Micromachining bulk glass by use of femtosecond laser pulses with nanojoule energy," Opt. Lett. 26,93-95 (2001). [CrossRef]
  5. L. F. Johnson and G. J. Guggenheim, "Infrared-Pumped Visible Laser," Appl. Phys. Lett. 19, 44-47 (1971). [CrossRef]
  6. L. Yang, Y. Dong, D. Chen, C. Wang, X. Hu, N. Da, G. Zhao, J. Xua, X. Jiang, C. Zhu, and J. Qiu, "Three-photon-excited upconversion luminescence of Ce3+: YAP crystal by femtosecond laser irradiation," Opt. Express 14, 243-247 (2006). [CrossRef] [PubMed]
  7. L. Yang, Y. Dong, D. Chen, C. Wang, N. Da, X. Jiang, C. Zhu, and J. Qiu, "Upconversion luminescence from 2E state of Cr3+ in Al2O3 crystal by infrared femtosecond laser irradiation," Opt. Express 13, 7893-98 (2005). [CrossRef] [PubMed]
  8. X. Meng, K. Tanaka, K. Fujita, and S. Murai, "Intense greenish emission from d0 transition metal ion Ti4+ in oxide glass," Appl. Phys. Lett. 90, 051917 (2007). [CrossRef]
  9. X. Meng, K. Tanaka, S. Murai, K. Fujita, K. Miura, and K. Hirao, "Two-photon-excited fluorescence from silicate glass containing tantalum ions pumped by a near-infrared femtosecond pulsed laser," Opt. Lett. 31, 2867-69 (2006). [CrossRef] [PubMed]
  10. S. Zhang, B. Zhu, S. Zhou, S. Xu, and J. Qiu, "Multi-photon absorption upconversion luminescence of a Tb3+-doped glass excited by an infrared femtosecond laser," Opt. Express 15,6883-88 (2007). [CrossRef] [PubMed]
  11. R. P. Chin, Y. R. Shen, and V. Petrova-koch, "Photoluminescence from porous silicon by infrared multiphoton excitation," Science 270, 776-778 (1995). [CrossRef]
  12. S. Juodkazis, A. V. Rode, E. G. Gamaly, S. Matsuo, and H. Misawa, "Recording and reading of three-dimensional optical memory in glasses," Appl. Phys. B: Lasers Opt. 77, 361-368 (2003). [CrossRef]
  13. S. H. Shin, D. Y. Jeon, and K. S. Suh, "Charge-transfer nature in luminescence of YNbO4: Bi blue phosphor," J. Appl. Phys. 90, 5986 (2001). [CrossRef]
  14. G. Blasse and F. van To1, "Luminescence of KNb3O8," Solid State Comm. 95,465- 468 (1995). [CrossRef]
  15. D. Chen, L. Yang, M. Peng, C. Wang, N. Da, Y. Qiao, Q. Zhou, C. Zhu, and T. Akai, "Preparation and fluorescent property of Eu-doped high silica glasses," J. Rare Earths 24, 191-195 (2006). [CrossRef]
  16. A. Aronne, V. N. Sigaev, B. Champagnon, E. Fanelli, V. Califano, L. Z. Usmanova, and P. Pernice, "The origin of nanostructuring in potassium niobiosilicate glasses by Raman and FTIR spectroscopy," J. Non-Cryst. Solids 351, 3610-3618 (2005). [CrossRef]

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