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Optics Express

Optics Express

  • Editor: Michael Duncan
  • Vol. 14, Iss. 1 — Jan. 9, 2006
  • pp: 243–247
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Three-photon-excited upconversion luminescence of Ce3+: YAP crystal by femtosecond laser irradiation

Luyun Yang, Yongjun Dong, Danping Chen, Chen Wang, Xiao Hu, Ning Da, Guangjun Zhao, Jun Xu, Xiongwei Jiang, Congshan Zhu, and Jianrong Qiu  »View Author Affiliations


Optics Express, Vol. 14, Issue 1, pp. 243-247 (2006)
http://dx.doi.org/10.1364/OPEX.14.000243


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Abstract

Infrared to ultraviolet and visible upconversion luminescence was demonstrated in trivalent cerium doped YAlO3 crystal (Ce3+: YAP) under focused infrared femtosecond laser irradiation. The fluorescence spectra show that the upconverted luminescence comes from the 5d-4f transitions of trivalent cerium ions. The dependence of luminescence intensity of trivalent cerium on infrared pumping power reveals that the conversion of infrared radiation is dominated by three-photon excitation process. It is suggested that the simultaneous absorption of three infrared photons pumps the Ce3+ ion into upper 5d level, which quickly nonradiatively relax to lowest 5d level. Thereafter, the ions radiatively return to the ground states, leading to the characteristic emission of Ce3+.

© 2006 Optical Society of America

1. Introduction

2. Experiment

Crystal of Ce: YAP with Ce3+ concentration of 0.5at% was grown by the Czochralski technique in an argon atmosphere. The high-purity Y2O3 (>99.999), CeO2 (>99.99) and Al2O3 (99.99%) powders were used as starting materials for growth. The apparatus and detailed crystal-growth procedure have been described elsewhere [17

17. G. J. Zhao, X. H. Zeng, S. M. Zhou, J. Xu, Y. L. Tian, and W. X. Huang, “Growth defects in czochraiski-grown Ce: YAlO3 scintillation crystals,” Phys. Status Solidi. A199, 186–191 (2003).

]. The crystal obtained was cut and polished into crystal samples with thickness of 1.5mm for subsequent femtosecond laser irradiation and spectral measurements.

A regeneratively amplified 800 nm Ti: sapphire laser that emits 120 femtosecond, 1 kHz, mode-locked pulses was used as pump source. The laser beam was focused into sample by an optical lens with focal length of 100mm. The position of the focal point was beneath the sample surface. The average power at the focused area was controlled below 19mW. The fluorescence spectra excited by focused femtosecond laser and 267nm monochromatic light from a xenon lamp were recorded by a spectrophotometer of ZOLIX SBP300 and JASCO FP6500, respectively. In addition, the absorption spectrum was measured with a JASCO V-570 spectrophotometer. All the measurements are preformed under room temperature.

3. Results and discussion

Under focused femtosecond laser irradiation, strong purple emission light was seen on the focused spot. Figure 1 shows the emission spectrum of the Ce3+: YAP irradiated by focused femtosecond laser. The Fig. 1 also contains a spectrum of Ce3+: YAP irradiated by 267nm monochromatic light from a xenon lamp.

Fig. 1. Emission spectra of Ce3+: YAP crystal under focused 800nm femtosecond laser irradiation and 267nm monochromatic light excitation.

The spectrum of Ce3+: YAP crystal irradiated by femtosecond laser is similar to that irradiated by 267nm monochromatic light. They both exhibit a broad emission band centered on 380nm. These results indicate that the emission of the Ce3+: YAP excited by femtosecond laser can be ascribed to the 5d-4f transitions of the Ce3+ ions. In fact, Ce3+ ions in YAP crystal reside at lattice sites having Clh symmetry. The 5d levels are extremely host sensitive and located in ultraviolet region. The lowest 5d state is 33 000 cm-1 above the 4F7/2 ground state. The transitions from ground states to 5d states are spin-allowed, corresponding to several strong absorption bands in Ce3+: YAP crystal. The measured absorption spectrum of Ce3+: YAP is shown in Fig. 2.

Fig. 2. Absorption spectrum of Ce3+: YAP crystal

These strong absorption bands usually act as efficient pumping bands. Excitation at ultraviolet bands can pump the Ce3+ ion into upper 5d levels, which quickly cascade down to the lowest 5d level. Thereafter, the ions radiatively relax to the ground states, creating broad 5d-4f emissions. At room temperature, the fluorescence appears as a broad band from 330nm to beyond 450nm with a peak at 380nm. From the above demonstration, it seems as if the focused infrared femtosecond laser can act as an ultraviolet source, producing a spatially confined irradiation in the interior of bulk of Ce3+: YAP crystal.

Generally, conversion of infrared radiation to the visible or ultraviolet emission involves multiphoton absorption process. The multiphoton absorption probability depends strongly on the laser intensity, leading to an exponential dependence of fluorescence intensity on the pumping power. The relationship between the pumping power and the fluorescence intensity can be described as [18

18. R. P. Chin, Y. R. Shen, and V. Petrova-koch, “Photoluminescence from Porous Silicon by Infrared Multiphoton Excitation,” Science. 270, 776–778 (1995). [CrossRef]

]:

IPn

Where, I is the integrated intensity of the upconversion luminescence, P is the average power of the pumping laser, and n is the photon number. The logarithmic transformation of the pumping power and fluorescence intensity is plotted in Fig. 3.

Fig. 3. Relationship between the fluorescence intensity of the 5d-4f transition of Ce3+ in YAP crystal and the pump power of femtosecond laser.

The number of photons n can be determined from the slope coefficient of the linear fitted line. The slope coefficient of the fitted line is 2.95, which indicates that the upconversion luminescence originates from three-photon absorption of 800nm infrared laser.

Upconversion processes of the solid materials containing rare earth ions with complicated 4f energy levels have been extensively investigated to clarify actual upconversion pump processes. Generally, the main upconversion mechanisms can be classified as energy transfer, excited-state absorption, cooperative upconversion, and photon avalanche [9–11

9. J. S. Chivian, W. E. Case, and D. D. Eden, “The photon avalanche: A new phenomenon in Pr3+ -based infrared quantum counters,” Appl. Phys. Lett. 35, 124–125 (1979). [CrossRef]

]. Since there is no any absorption band from 380 to 850nm in the absorption spectrum of the Ce3+: YAP crystal, and no optical breakdown and no detectable change of the absorption before and after femtosecond laser irradiation on this irradiation condition, the upconversion luminescence is not due to energy transfer, excited-state absorption, cooperative upconversion and photon avalanche. It is also not a femtosecond laser induced defect-assisted process.

It is worth noting that the three-photon excited upconversion luminescence is not limited to Ce3+: YAP crystal. We have also examined the upconversion behavior of several other Ce3+ doped crystals such as Ce3+: GSO, Ce3+: YSO. These crystals have strong emission in blue region by 800nm femtosecond laser irradiation. The quantitative research on the conversion efficiency of upconversion emission in these crystals is under investigation.

4. Conclusions

In summary, the ultraviolet and visible upconversion luminescence in Ce3+ YAP has been observed under focused infrared femtosecond laser irradiation. The dependence of the fluorescence intensity of the Ce3+ on the pump power shows that the upconversion luminescence is dominated by three- photon absorption process. The analysis reveals that the absorption of three photons is simultaneous rather than sequential. This result provides a promising method to obtain ultraviolet or visible emission from infrared pumping light in solid-state crystals, and has potential applications in visible lasers, high-resolution optical data storage, three-dimensional displays, etc.

Acknowledgments

The authors would like to acknowledge the financial support provided by the National Natural Science Foundation of China under the grant number of 60377040. This work has also been supported by Shanghai Committee of Science and Technology (04XD14018 and 0352nm042).

References and links

1.

G. S. He, P. P. Markowicz, T. C. Lin, and P. N. Prasad, “Observation of stimulated emission by direct three-photon excitation,” Nature. 415, 767–770 (2002). [CrossRef] [PubMed]

2.

J. S. Marchant, G. E. Stutzmann, M. A. Leissring, F. M. LaFerla, and I. Parker, “Multiphoton-evoked color change of DsRed as an optical highlighter for cellular and subcellular labeling,” Nature Biotechnology. 19, 645–649 (2001). [CrossRef] [PubMed]

3.

K. Svoboda, W. Denk, D. Kleinfeld, and D.W. Tank, “In vivo dendritic calcium dynamics in neocortical pyramidal neurons,” Nature. 385, 161–165 (1997). [CrossRef] [PubMed]

4.

G. S. He, J.M. Dai, T.C. Lin, P. P. Markowicz, and P. N. Prasad, “Ultrashort 1.5-μm laser excited upconverted stimulated emission based on simultaneous three-photon absorption,” Opt Lett. 28, 719–721 (2003). [CrossRef] [PubMed]

5.

S. Kawata, H. B. Sun, T. Tanaka, and K. Takada, “Finer features for functional microdevices,” Nature. 412, 697–698 (2001). [CrossRef] [PubMed]

6.

H. You and M. Nogami, “Three-photon-excited fluorescence of Al2O3-SiO2 glass containing Eu3+ ions by femtosecond laser irradiation,” Appl. Phys. Lett. 84, 2076–78 (2004). [CrossRef]

7.

J. Qiu, P. G. Kazansky, J. Si, K. Miura, T. Mitsuyu, K. Hirao, and A. L. Gaeta, “Memorized polarization-dependent light scattering in rare-earth-ion-doped glass,”Appl. Phys. Lett. 77, 1940–42 (2000). [CrossRef]

8.

P. G. Kazansky, H. Inouye, T. Mitsuyu, K. Miura, J. Qiu, and K. Hirao, “Anomalous anisotropic light scattering in Ge-doped silica glass,” Phys. Rev. Lett. 82, 2199–2202 (1999). [CrossRef]

9.

J. S. Chivian, W. E. Case, and D. D. Eden, “The photon avalanche: A new phenomenon in Pr3+ -based infrared quantum counters,” Appl. Phys. Lett. 35, 124–125 (1979). [CrossRef]

10.

N. Bloembergen, “Solid State Infrared Quantum Counters,” Phys. Rev. Lett. 2, 84–85 (1959). [CrossRef]

11.

F. E. Auzel, “Upconversion and Anti-Stokes Processes with f and d Ions in Solids,” Chem. Rev. (Washington, D.C.) 104, 139–174 (2004). [CrossRef] [PubMed]

12.

L.Y. Yang, Y. J. Dong, D. P. Chen, C. Wang, N. Da, X. W. Jiang, C. S. Zhu, and J. R. Qiu, “Upconversion luminescence from 2E state of Cr3+ in Al2O3 crystal by infrared femtosecond laser irradiation,” Opt. Express. 13, 7893–98 (2005), http://www.opticsinfobase.org/abstract.cfm?id=85711 [CrossRef] [PubMed]

13.

M. J. Weber, “Inorganic scintillators: today and tomorrow,” J. Luminescence. 100, 35–44 (2002). [CrossRef]

14.

S. Baccaro, K. Blazek, F. de Notaristefani, P. Maly, J. A. Mares, R. Pani, R. Pellegrini, and A. Soluri, “Scintillation properties of YAP:Ce,” Nucl. Instr. Meth. A361, 209–215 (1995).

15.

R. Autrata, P. Schauer, Ji. Kvapil, and Jos. Kvapil, “Cathodoluminescence efficiency of Y3Al5O12 and YAlO3 single crystal in dependence on Ce3+ and other dopants concentrations,”Cryst. Res. Technol. 18, 907 (1983). [CrossRef]

16.

R. Autrata, P. Schauer, Ji. Kvapil, and Jos. Kvapil, “A Single crystal of YAlO3:Ce3+ as a fast scintillator in SEM,” Scanning , 5, 91–96 (1983). [CrossRef]

17.

G. J. Zhao, X. H. Zeng, S. M. Zhou, J. Xu, Y. L. Tian, and W. X. Huang, “Growth defects in czochraiski-grown Ce: YAlO3 scintillation crystals,” Phys. Status Solidi. A199, 186–191 (2003).

18.

R. P. Chin, Y. R. Shen, and V. Petrova-koch, “Photoluminescence from Porous Silicon by Infrared Multiphoton Excitation,” Science. 270, 776–778 (1995). [CrossRef]

OCIS Codes
(140.7090) Lasers and laser optics : Ultrafast lasers
(190.4180) Nonlinear optics : Multiphoton processes
(190.7220) Nonlinear optics : Upconversion

ToC Category:
Nonlinear Optics

Citation
Luyun Yang, Yongjun Dong, Danping Chen, Chen Wang, Xiao Hu, Ning Da, Guangjun Zhao, Jun Xu, Xiongwei Jiang, Congshan Zhu, and Jianrong Qiu, "Three-photon-excited upconversion luminescence of Ce3+: YAP crystal by femtosecond laser irradiation," Opt. Express 14, 243-247 (2006)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-14-1-243


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References

  1. G. S. He, P. P. Markowicz, T. C. Lin, and P. N. Prasad, "Observation of stimulated emission by direct three-photon excitation," Nature. 415, 767-770 (2002). [CrossRef] [PubMed]
  2. J. S. Marchant, G. E. Stutzmann, M. A. Leissring, F. M. LaFerla, and I. Parker, "Multiphoton-evoked color change of DsRed as an optical highlighter for cellular and subcellular labeling," Nature Biotechnology. 19, 645-649 (2001). [CrossRef] [PubMed]
  3. K. Svoboda, W. Denk, D. Kleinfeld, and D.W.Tank, "In vivo dendritic calcium dynamics in neocortical pyramidal neurons," Nature. 385, 161-165 (1997). [CrossRef] [PubMed]
  4. G. S. He, J.M. Dai, T.C. Lin, P. P. Markowicz, P. N. Prasad, "Ultrashort 1.5-µm laser excited upconverted stimulated emission based on simultaneous three-photon absorption," Opt Lett. 28, 719-721 (2003). [CrossRef] [PubMed]
  5. S. Kawata, H. B. Sun, T. Tanaka, and K. Takada, "Finer features for functional microdevices," Nature. 412, 697-698 (2001). [CrossRef] [PubMed]
  6. H. You and M. Nogami, "Three-photon-excited fluorescence of Al2O3-SiO2 glass containing Eu3+ ions by femtosecond laser irradiation," Appl. Phys. Lett. 84, 2076-78 (2004). [CrossRef]
  7. J. Qiu, P. G. Kazansky, J. Si, K. Miura, T. Mitsuyu, K. Hirao, A. L. Gaeta, "Memorized polarization-dependent light scattering in rare-earth-ion-doped glass,"Appl. Phys. Lett. 77, 1940-42 (2000). [CrossRef]
  8. P. G. Kazansky, H. Inouye, T. Mitsuyu, K. Miura, J. Qiu, and K. Hirao, "Anomalous anisotropic light scattering in Ge-doped silica glass," Phys. Rev. Lett. 82, 2199-2202 (1999). [CrossRef]
  9. J. S. Chivian, W. E. Case, and D. D. Eden, "The photon avalanche: A new phenomenon in Pr3 + -based infrared quantum counters," Appl. Phys. Lett. 35, 124-125 (1979). [CrossRef]
  10. Bloembergen. N, "Solid State Infrared Quantum Counters," Phys. Rev. Lett. 2, 84-85 (1959). [CrossRef]
  11. F. E. Auzel, "Upconversion and Anti-Stokes Processes with f and d Ions in Solids," Chem. Rev. (Washington, D.C.) 104, 139-174 (2004). [CrossRef] [PubMed]
  12. L.Y. Yang, Y. J. Dong, D. P. Chen, C. Wang, N. Da, X. W. Jiang, C. S. Zhu, J. R. Qiu, "Upconversion luminescence from 2E state of Cr3+ in Al2O3 crystal by infrared femtosecond laser irradiation," Opt. Express. 13, 7893-98 (2005),<a href=-" http://www.opticsinfobase.org/abstract.cfm?id=85711"> http://www.opticsinfobase.org/abstract.cfm?id=85711</a> [CrossRef] [PubMed]
  13. M. J. Weber, "Inorganic scintillators: today and tomorrow," J. Luminescence. 100, 35-44 (2002). [CrossRef]
  14. S. Baccaro, K. Blazek, F. de Notaristefani, P. Maly, J. A. Mares, R. Pani, R. Pellegrini and A. Soluri, "Scintillation properties of YAP:Ce," Nucl. Instr. Meth. A361, 209-215 (1995).
  15. R. Autrata, P. Schauer, Ji. Kvapil, and Jos. Kvapil, "Cathodoluminescence efficiency of Y3Al5O12 and YAlO3 single crystal in dependence on Ce3+ and other dopants concentrations,"Cryst. Res. Technol. 18, 907 (1983). [CrossRef]
  16. R. Autrata, P. Schauer, Ji. Kvapil, and Jos. Kvapil, "A Single crystal of YAlO3:Ce3+ as a fast scintillator in SEM," Scanning, 5, 91-96 (1983). [CrossRef]
  17. G. J. Zhao, X. H. Zeng, S. M. Zhou, J. Xu, Y. L. Tian, and W. X. Huang, "Growth defects in czochraiski-grown Ce: YAlO3 scintillation crystals," Phys. Status Solidi. A199, 186-191 (2003).
  18. R. P. Chin, Y. R. Shen, and V. Petrova-koch, "Photoluminescence from Porous Silicon by Infrared Multiphoton Excitation," Science. 270, 776-778 (1995). [CrossRef]

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