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Optics Express

Optics Express

  • Editor: Michael Duncan
  • Vol. 13, Iss. 25 — Dec. 12, 2005
  • pp: 10157–10162
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Three-photon-excited upconversion luminescence of YVO4 single crystal by infrared femtosecond laser irradiation

Luyun Yang, Chen Wang, Yongjun Dong, Ning Da, Xiao Hu, Danping Chen, and Jianrong Qiu  »View Author Affiliations


Optics Express, Vol. 13, Issue 25, pp. 10157-10162 (2005)
http://dx.doi.org/10.1364/OPEX.13.010157


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Abstract

We report on the upconversion luminescence of a pure YVO4 single crystal excited by an infrared femtosecond laser. The luminescent spectra show that the upconversion luminescence comes from the transitions from the lowest excited states 3T1, 3T2 to the ground state 1A1 of the VO43. 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 simultaneous absorption of three infrared photons promotes the VO43 to excited states, which quickly cascade down to lowest excited states, and radiatively relax to ground states, resulting in the broad characteristic fluorescence of VO43.

© 2005 Optical Society of America

1. Introduction

2. Experiment

Crystal of YVO4 was grown by czochralski method. The starting materials of high purity Y2O3, and V2O5 were used to synthesize stoichiometric YVO4. The apparatus and detailed crystal-growth procedure have been described elsewhere [14

14 . L. H. Zhang , Y. Hang , D. L. Sun , B. X. Qian , F. S. Li , and S. T. Yin , “ The color problems of YVO 4 crystal ,” J. Synth. Cryst. 32 , 24 – 26 ( 2003 in chinese).

]. The crystal obtained was cut and polished into samples with various thickness from 1mm to 4mm for femtosecond laser irradiation and spectral measurements. The crystal samples were yellow. No inclusions or other light scattering centers were observed by the optical microscope.

A regeneratively amplified 800 nm Ti: sapphire laser that emits 120 femtosecond, 1 kHz, mode-locked pulses was used as the irradiation source. To achieve a high power density, the laser beam was focused into samples by objective lens or optical lens. When using objective lens, the focal point can be monitored by a confocal microscope system linked to a charge coupled device system. The position of the focal point was beneath the sample surface. In fact, the laser beam can be focused into any place within the sample. The spot size can be controlled at least below several microns by choosing appropriate objective lens or optical lens and adjusting the power density of laser beam. The fluorescence spectra excited by focused femtosecond laser were recorded by a spectrophotometer of ZOLIX SBP300. The scanning rate of this spectrophotometer was 100nm/min. The fluorescence spectra were measured at ~90° direction with respect to the pump beam. The fluorescence spectra excited by a 267nm monochromatic light from a xenon lamp were measured by a JASCO FP6500 spectrophotometer. In addition, the absorption spectra were obtained by a JASCO V-570 spectrophotometer. All the measurements were preformed under room temperature.

Under focused femtosecond laser irradiation, strong blue emission was seen near the focused spot by naked eyes. The emission spectrum irradiated by the femtosecond laser with a power density of 5.6TW/cm2 is shown in Fig. 1. The laser beam was focused by an optical lens with focal length of 100mm. The thickness of the sample used was 1.5mm. The Fig. 1 also shows the luminescent spectrum of YVO4 irradiated by 267nm monochromatic light from a xenon lamp. The inset in Fig. 1 is a photograph of the crystal sample irradiated by focused femtosecond laser. The brightest spot in the middle of the crystal corresponds to the place irradiated by femtosecond laser. The two bright spots on the edges of the crystal are the light scattering spots.

Fig. 1. Emission spectra of the YVO4 crystal sample under focused femtosecond laser irradiation and 267nm monochromatic light excitation. The inset was the photograph of the YVO4 crystal sample irradiated by focused femtosecond laser, which was taken in darkroom.

The spectrum of YVO4 crystal irradiated by the femtosecond laser exhibits a broad emission band peaking at 438nm and a shoulder peak at 464nm, which is similar to those of YVO4 crystal excited by 267nm monochromatic light. All these peaks can be assigned to the characteristic emission of YVO4 single crystal.

For vanadate group in YVO4 single crystal, there are one ground state of 1A1 with configuration t16e0t20, and four excited states of 3T1, 3T2, 1T1, and 1T2 with configuration t15e1t20 [10

10 . H. Ronde and G. Blasse ,“ The nature of the electronic transitions of the vanadate group ,” J. Inorg. Nuclear Chem. 40 , 215 ( 1978 ). [CrossRef]

.11

11 . W. Barendswaard , R. T. Weber , and J. H. van der Waals , “ An EPR study of the luminescent triplet state of VO43 in YVO 4 and YP 0.96 V 0.04 O 4 single crystals at 1.2 K ,” J. Chem. Phys. 87 , 3731 ( 1987 ). [CrossRef]

]. The transitions from 1A1 (t16e0t20) to 1T1 (t15e1t20) and 1T2 (t15e1t20) are allowed by an electric dipole mechanism, which correspond to two absorption bands in absorption spectrum of YVO4 crystal.

Fig. 2. Absorption spectrum and the excitation spectrum (the inset) of the YVO4 crystal sample.

Figure 2 shows the absorption spectrum of YVO4 crystal. This spectrum shows a strong absorption band below 350nm, which is a superposition of the intrinsic absorption of YVO4 crystal and the absorption of vanadate group. To manifest the absorption of vanadate group, we measured the excitation spectrum of vanadate group by monitoring the fluorescence at 443nm. The excitation spectrum clearly presents two strong absorption bands. These two bands usually act as efficient pumping bands [12

12 . Chang Hsu and Richard C. Powell , “ Energy transfer in europium doped yttrium vanadate crystals ,” J. Luminescence. 10 , 273 – 293 ( 1975 ). [CrossRef]

]. Exciting any of these bands produces electron population in excited states of 1T1, and 1T2. Then, the electrons can nonradiatively relax to the lowest excited states of 3T1, and 3T2, from which, the characteristic emission occurs. At room temperature, the fluorescence appears as broad bands from 350nm to 650nm. From the above results, it seems that the focused infrared femtosecond laser may act as a spatially confined ultraviolet source in the interior of bulk of YVO4 crystal.

Generally, conversion of infrared radiation to the visible emission can be ascribed to a multiphoton absorption process. The relationship between the pumping power density and the fluorescence intensity can be described as [15

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

]:

IIinn

Where, I is the integrated intensity of the upconversion luminescence, I in is the pump power density of the infrared laser, and n is the photon number. The number of photons must satisfy that the total energy of n photons exceeds or equals to the excitation energy required by excited states. The n can be experimentally determined from the slope coefficient of linear fitted line of logarithmic plot of the pumping power density and fluorescence intensity. The pumping power density was controlled below 25TW/cm2. No degradation of the PL or damage to the sample was observed. The log-log relationship between pumping power density of femtosecond laser and fluorescence intensity of YVO4 crystal is shown in Fig. 3. It can be seen that the slope coefficient of the fitted line is 2.93. Similar results were obtained by using the samples with thickness of 2mm; 3mm and 4mm.These results indicate that the upconversion may be a three-photon absorption process.

Fig. 3. Fluorescence intensity of the transition from 3T1, and 3T2 to 1A1 of VO43 as function of the femtosecond laser pump power density.

Due to the high peak power of the femtosecond laser, the effect of self-focusing should be taken into consideration when we discuss the dependence between the luminescence intensity and pump power density. The critical power for causing self-focusing can be estimated to be ~106 W for YVO4 crystal. The peak power of the laser we used for the experiments is almost 107 W, higher than the critical power for self-focusing. However, from our experiments, we got the similar value of slope coefficient n even when we use various samples with different thickness and optical lens with focal length of 50mm. It indicates that the effect of surface and self-focusing which may have influence on the luminescent behavior is not dominant in the upconversion process.

4. Conclusions

In summary, we have experimentally demonstrated upconversion luminescence in pure YVO4 single crystal by using 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 analysis reveals that the absorption of three photons is simultaneous rather than sequential. This result provides an efficient route to produce upconversion luminescence in intrinsic luminescence materials, and has potential applications in visible lasers, optical data storage, three-dimensional displays, etc.

Acknowledgments

This work is supported by National Natural Science Foundation of China (Grants No.50125258 and No.60377040), and by Shanghai Nanotechnology Promote Center (Grants No. 0352nm042 and No.04XD14018). We thank Dr. C. J. Zhao, Q. T. Zhao, and X. W. Jiang for enlightening discussions.

References and links

1 .

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

2 .

D. A. Parthenopoulos and P. M. Rentzepis , “ Three-dimensional optical storage memory ,” Science. 245 , 843 – 845 ( 1989 ). [CrossRef] [PubMed]

3 .

E. Downing , L. Hesselink , J. Ralston , and R. Macfarlane , “ A Three-Color, Solid-State, Three-Dimensional Display ,” Science. 273 , 1185 – 1189 ( 1996 ). [CrossRef]

4 .

W. Denk , J. H. Strickler , and W. W. Webb . “ Two-photon laser scanning fluorescence microscope ,” Science. 248 , 73 – 76 ( 1990 ). [CrossRef] [PubMed]

5 .

J. S. Chivian , W. E. Case , and D. D. Eden , “ The photon avalanche: A new phenomenon in Pr 3+ -based infrared quantum counters ,” Appl. Phys. Lett. 35 , 124 – 125 ( 1979 ). [CrossRef]

6 .

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

7 .

S. Heer , M. Wermuth , K. Krämer , and H. U. Güdel , “ Upconversion excitation of Cr 3+2 E emission in Y 3 Ga 5 O 12 codoped with Cr 3+ and Yb 3+ ,” Chem. Phys. Lett. 334 , 293 – 297 ( 2001 ). [CrossRef]

8 .

W. Kaiser and C.G.B. Garrett , “ Two-Photon Excitation in CaF 2 : Eu 2+ ,” Phys. Rev. Lett. 7 , 229 – 231 ( 1961 ). [CrossRef]

9 .

G. Blasse and B. C. Grabmaier , Luminescent Materials . ( Springer-Verlag, Berlin , 1994 ). [CrossRef]

10 .

H. Ronde and G. Blasse ,“ The nature of the electronic transitions of the vanadate group ,” J. Inorg. Nuclear Chem. 40 , 215 ( 1978 ). [CrossRef]

11 .

W. Barendswaard , R. T. Weber , and J. H. van der Waals , “ An EPR study of the luminescent triplet state of VO43 in YVO 4 and YP 0.96 V 0.04 O 4 single crystals at 1.2 K ,” J. Chem. Phys. 87 , 3731 ( 1987 ). [CrossRef]

12 .

Chang Hsu and Richard C. Powell , “ Energy transfer in europium doped yttrium vanadate crystals ,” J. Luminescence. 10 , 273 – 293 ( 1975 ). [CrossRef]

13 .

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 Cr 3+ in Al 2 O 3 crystal by infrared femtosecond laser irradiation ,” Opt. Express. 13 , 7893 – 98 ( 2005 ). [CrossRef] [PubMed]

14 .

L. H. Zhang , Y. Hang , D. L. Sun , B. X. Qian , F. S. Li , and S. T. Yin , “ The color problems of YVO 4 crystal ,” J. Synth. Cryst. 32 , 24 – 26 ( 2003 in chinese).

15 .

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

16 .

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

17 .

Richard Scheps , “ Upconversion laser processes ,” Prog. Quantum Electron. 20 , 271 – 358 ( 1996 ). [CrossRef]

18 .

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]

19 .

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 ,” Nat. Biotechnol. 19 , 645 – 649 ( 2001 ). [CrossRef] [PubMed]

20 .

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]

21 .

H. You and M. Nogami , “ Three-photon-excited fluorescence of Al 2 O 3 -SiO 2 glass containing Eu 3+ ions by femtosecond laser irradiation ,” Appl. Phys. Lett. 84 , 2076 – 78 ( 2004 ). [CrossRef]

22 .

H. You and M. Nogami , “ Upconversion luminescence of Al 2 O 3 –SiO 2 :Ce 3+ glass by femtosecond laser irradiation ,” Appl. Phys. Lett. 85 , 3432 – 34 ( 2004 ) [CrossRef]

23 .

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]

24 .

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]

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

ToC Category:
Research Papers

Citation
Luyun Yang, Chen Wang, Yongjun Dong, Ning Da, Xiao Hu, Danping Chen, and Jianrong Qiu, "Three-photon-excited upconversion luminescence of YVO4 single crystal by infrared femtosecond laser irradiation," Opt. Express 13, 10157-10162 (2005)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-13-25-10157


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References

  1. L. F. Johnson, G. J. Guggenheim, "Infrared-pumped visible laser," Appl. Phys. Lett. 19, 44-47 (1971). [CrossRef]
  2. D. A. Parthenopoulos and P. M. Rentzepis, "Three-dimensional optical storage memory," Science 245, 843-845 (1989). [CrossRef] [PubMed]
  3. E. Downing, L. Hesselink, J. Ralston, and R. Macfarlane, "A three-color, solid-state, three-dimensional display," Science 273, 1185-1189 (1996). [CrossRef]
  4. W. Denk, J. H. Strickler, and W. W. Webb, "Two-photon laser scanning fluorescence microscope," Science 248, 73-76 (1990). [CrossRef] [PubMed]
  5. 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]
  6. F. E. Auzel, "Upconversion and anti-Stokes processes with f and d ions in solids," Chem. Rev. (Washington, D.C.) 104, 139-174 (2004).
  7. S. Heer, M. Wermuth, K. Krämer, and H. U. Güdel, "Upconversion excitation of Cr3+ 2E emission in Y3Ga5O12 codoped with Cr3+ and Yb3+," Chem. Phys. Lett. 334, 293-297 (2001). [CrossRef]
  8. W. Kaiser, and C. G. B.Garrett, "Two-photon excitation in CaF2: Eu2+," Phys. Rev. Lett. 7, 229-231 (1961). [CrossRef]
  9. G. Blasse and B. C. Grabmaier, Luminescent Materials (Springer-Verlag, Berlin, 1994). [CrossRef]
  10. H. Ronde and G. Blasse, "The nature of the electronic transitions of the vanadate group," J. Inorg. Nuclear Chem. 40, 215 (1978). [CrossRef]
  11. W. Barendswaard, R. T. Weber, and J. H. van der Waals, "An EPR study of the luminescent triplet state of VO4 3- in YVO4 and YP0.96V0.04O4 single crystals at 1.2 K," J. Chem. Phys. 87, 3731 (1987). [CrossRef]
  12. C. Hsu and R. C. Powell, "Energy transfer in europium doped yttrium vanadate crystals," J. Luminescence 10, 273-293 (1975). [CrossRef]
  13. 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). [CrossRef] [PubMed]
  14. L. H. Zhang, Y. Hang, D. L. Sun, B. X. Qian, F. S. Li, and S. T. Yin, "The color problems of YVO4 crystal," J. Synth. Cryst. 32, 24-26 (2003 in Chinese).
  15. R. P. Chin, Y. R. Shen, and V. Petrova-Koch, "Photoluminescence from porous silicon by infrared multiphoton excitation," Science 270, 776-778 (1995). [CrossRef]
  16. N. Bloembergen, "Solid state infrared quantum counters," Phys. Rev. Lett. 2, 84-85 (1959). [CrossRef]
  17. R. Scheps, "Upconversion laser processes," Prog. Quantum Electron. 20, 271-358 (1996). [CrossRef]
  18. 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]
  19. 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," Nat. Biotechnol. 19, 645-649 (2001). [CrossRef] [PubMed]
  20. 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]
  21. H. You and M. Nogami, "Three-photon-excited fluorescence of Al2O3-SiO2 glass containing Eu3+ ions by femtosecond laser irradiation," Appl. Phys. Lett. 84, 2076-2078 (2004). [CrossRef]
  22. H. You and M. Nogami, "Upconversion luminescence of Al2O3-SiO2:Ce3+ glass by femtosecond laser irradiation," Appl. Phys. Lett. 85, 3432-34 (2004). [CrossRef]
  23. 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, 1940-1942 (2000). [CrossRef]
  24. 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]

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