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Optics Express

Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 19, Iss. 20 — Sep. 26, 2011
  • pp: 19473–19479
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Ce-Tb-Mn co-doped white light emitting glasses suitable for long-wavelength UV excitation

Yang Yu, Zijun Liu, Nengli Dai, Yubang Sheng, Huaixun Luan, Jinggang Peng, Zuowen Jiang, Haiqing Li, Jinyan Li, and Luyun Yang  »View Author Affiliations


Optics Express, Vol. 19, Issue 20, pp. 19473-19479 (2011)
http://dx.doi.org/10.1364/OE.19.019473


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Abstract

We report on a new kind of white light emitting glass suitable for long-wavelength ultraviolet excitation by simultaneously emitting blue, green and red fluorescence, which is fabricated by melting of Ce3+-Tb3+-Mn2+ co-doped borosilicate glass. The spectroscopic properties of singly, doubly and triply doped glasses have been reported and the energy transfer from Ce3+ to Tb3+ and Mn2+ has also been investigated. By adjusting the concentration of different co-dopants, we obtained the ideal white light emitting borosilicate glass with the color coordinate (x = 0.318, y = 0.333).

© 2011 OSA

1. Introduction

Recently, white light-emitting diodes (W-LEDs) have attracted considerable attention due to their excellent advantages such as compact size, longer lifetime, energy saving, better reliability and environment protection. The W-LEDs have been regarded as the fourth generation of solid-state light sources [1

1. M. Jayasimhadri, K. Jang, H. S. Lee, B. Chen, S. S. Yi, and J. H. Jeong, “White light generation from Dy3+-doped ZnO–B2O3–P2O5 glasses,” J. Appl. Phys. 106(1), 13105 (2009). [CrossRef]

3

3. J. Wang, Z. Zhang, M. Zhang, Q. Zhang, Q. Su, and J. Tang, “The energy transfer from Eu2+ to Tb3+ in Ca10K (PO4) 7 and its application in green light emitting diode,” J. Alloy. Comp. 488(2), 582–585 (2009). [CrossRef]

]. At present, the W-LEDs consisting of a blue InGaN LED chip and yellow-emitting YAG: Ce3+ phosphors have been commercialized due to their easy fabrication, low cost, and high brightness. However, there are some inherent drawbacks such as poor color rendering index, poor emission homogeneity, and lower reproducibility in these white-LEDs. In addition, the emission color is largely determined by the input power, the luminescence properties of the phosphors and the phosphors coating thickness. Considerable investigations have been directed to tricolor phosphors for W-LEDs due to the recent development of near-UV LED chips [2

2. Z. Liu, N. Dai, H. Luan, Y. Sheng, J. Peng, Z. Jiang, H. Li, L. Yang, and J. Li, “Enhanced green luminescence in Ce-Tb-Ca codoped sintered porous glass,” Opt. Express 18(20), 21138–21146 (2010). [CrossRef] [PubMed]

5

5. M. Peng and L. Wondraczek, “Orange‐to‐Red Emission from Bi2+ and Alkaline Earth Codoped Strontium Borate Phosphors for White Light Emitting Diodes,” J. Am. Ceram. Soc. 93, 1437–1442 (2010).

]. Compared with the conventional phosphors, luminescent glasses are promising phosphor candidates for W-LEDs due to their specific advantages such as easy formation of any shape, higher transparency, simpler manufacture procedure and environment protection. Researches on luminescent glasses primarily focused on phosphate and borate based glasses in that rare earth and transition metal ions can be dissolved much more without heavily concentration quenching [6

6. L. Yang, N. Dai, Z. Liu, Z. Jiang, J. Peng, H. Li, J. Li, M. Yamashita, and T. Akai, “Tailoring of clusters of active ions in sintered nanoporous silica glass for white light luminescence,” J. Mater. Chem. (2011).

8

8. R. Martínez-Martínez, A. Speghini, M. Bettinelli, C. Falcony, and U. Caldiño, “White light generation through the zinc metaphosphate glass activated by Ce3+, Tb3+ and Mn2+ ions,” J. Lumin. 129(11), 1276–1280 (2009). [CrossRef]

]. However, the poor chemical stability as well as the physical properties of these glasses limited their application. Borosilicate glasses are appropriate host materials for rare earth ions and transition metal ions due to their easy access of raw materials, lower melting temperature, excellent chemical stability and physical properties and higher transparency in UV and visible region [9

9. L. Yang, M. Yamashita, and T. Akai, “Green and red high-silica luminous glass suitable for near-ultraviolet excitation,” Opt. Express 17(8), 6688–6695 (2009). [CrossRef] [PubMed]

, 10

10. S. Liu, G. Zhao, X. Lin, H. Ying, J. Liu, J. Wang, and G. Han, “White luminescence of Tm-Dy ions co-doped aluminoborosilicate glasses under UV light excitation,” J. Solid State Chem. 181(10), 2725–2730 (2008). [CrossRef]

]. In this manuscript, we report on a new kind of Ce-Tb-Mn co-doped long-wavelength ultraviolet (346nm) excited white light emitting borosilicate luminescent glass. The color coordinate (x = 0.318, y = 0.333) is very close to the ideal white light. In these co-doped glasses, Ce3+ acts as a blue emitter as well as a donor transferring part of its excitation energy to Tb3+ and Mn2+ acceptors, which can emit green and red fluorescence, respectively.

2. Experiment

The borosilicate glass samples have the composition of 50SiO2-14B2O3-8MgO-8ZnO-3.5ZrO2-3Na2O-0.4Gd2O3-0.03Sb2O3-10Al2O3-xCeO2-yTb2O3-zMnO. The raw materials are analytical grade and chosen from corresponding oxides and carbonates. The reduction atmosphere is necessary to keep the doped ions in the appropriate valence state, which is realized by addition of carbon powder around the batch. The batches are put in corundum crucible and melted for two hours at 1580°C in a reduction atmosphere. Then, the melts were poured on the pre-heated steel mold and annealed for 2h at 550°C to obtain the final glasses.

3. Results and discussion

Figure 1
Fig. 1 The UV-visible absorption spectra of the host, the Tb3+ doped, Ce3+ doped, Mn2+ doped and Ce3+– Tb3+–Mn2+ co-doped melting borosilicate glasses. The inset shows the absorption band about 415nm. The Ce3+ doped glass has a Ce3+ concentration of 0.8 mol%. The Tb3+ doped glass has a Tb3+ concentration of 0.8 mol%. The Mn2+ doped glass has a Mn2+ concentration of 1.5 mol%. The Ce3+-Tb3+-Mn2+ co-doped glass has the same concentration with the single doped glasses.
shows the UV-visible absorption spectra of the host (SiB), the Tb3+ single doped (Tb), the Ce3+ single doped (Ce), the Mn2+ single doped (Mn) and the Ce3+– Tb3+–Mn2+ co-doped (CTM) borosilicate glasses. The inset shows the absorption spectra around 415nm. The host has only a strong absorption band near 200nm corresponding to its intrinsic absorption. It is shown from the spectra that the UV absorption cut-off wavelength of Ce3+ doped glass is obviously red-shifted compared with the host glass due to the allowed 4f→5d transition of Ce3+ ions. As for the Tb3+ doped glass, the absorption spectra is similar to the host and the UV cut-off wavelength is a little red-shifted corresponding to the electronic transitions from the 7F6 ground state to the higher excited state. For the Mn2+ doped glass, the UV absorption cut-off wavelength is very close to the host glasses and the inset suggested that there is a Mn2+ absorption band around 415nm ascribed to its intrinsic absorption. It shows that there is a high absorbance in the near ultraviolet region by comparing the absorption spectra of the host and the sample co-doped with Ce3+, Tb3+ and Mn2+ ions (CTM). The co-doped sample has an absorption band centered at 415nm corresponding to the intrinsic absorption of Mn2+ ions [7

7. L. Huang, X. Wang, H. Lin, and X. Liu, “Luminescence properties of Ce3+ and Tb3+ doped rare earth borate glasses,” J. Alloy. Comp. 316(1-2), 256–259 (2001). [CrossRef]

, 11

11. J. C. Zhang, C. Parent, G. Le Flem, and P. Hagenmuller, “White light emitting glasses,” J. Solid State Chem. 93(1), 17–29 (1991). [CrossRef]

, 12

12. T. Tsuboi, “Optical properties of Ce3+/Tb3+-codoped borosilicate glass,” EPJ Appl. Phys. (Berl.) 26, 95–101 (2004). [CrossRef]

]. Moreover, these glasses have high optical transparency due to their low absorptivity in the visible region, which is essential for the realization of high fluorescent quantum yields.

To manifest the absorption and the fluorescence of Ce3+, Tb3+, Mn2+ ions, we measured the emission and the excitation spectra of the single doped glasses shown in Fig. 2
Fig. 2 Emission spectra (black) and excitation spectra (red) of Ce3+-doped (2a), Tb3+-doped (2b), Mn2+ -doped (2c) and the combination of the excitation spectrum (blue) of Ce3+-doped and the emission spectra (green and red) of Tb3+-doped and Mn2+ doped (2d) borosilicate glasses. For the single doped samples the excitation wavelengths are 346nm, 368nm and 417nm, respectively, and the monitoring wavelengths are 405nm, 548nm and 607nm, respectively. The Ce3+ -doped glass has a Ce3+ concentration of 0.8 mol%. The Tb3+-doped glass has a Tb3+ concentration of 0.8 mol%. The Mn2+-doped glass has a Mn2+ concentration of 1.5 mol%.
. Figure 2(a), Fig. 2(b), and Fig. 2(c) show the emission spectrum (black) and the excitation spectrum (red) of cerium-doped, terbium-doped, and manganese-doped borosilicate glasses, respectively. Figure 2d shows the emission spectrum of cerium-doped (blue), the excitation spectra (green and red) of terbium-doped and manganese-doped borosilicate glasses. The excitation wavelengths for Ce3+ doped, Tb3+ doped and Mn2+ doped glasses are 346nm, 368nm and 417nm, respectively. The monitoring wavelengths for Ce3+ doped, Tb3+ doped and Mn2+ doped glasses are 405nm, 548nm and 607nm, respectively.

For the Ce3+ single doped borosilicate glass (2a), there is a broad asymmetric blue emission band from about 350 nm to 500 nm under an UV excitation at 346 nm, which can be ascribed to the parity-allowed transitions of the lowest component of the 5d state to 2F5/2 and 2F7/2 levels of Ce3+ ions [6

6. L. Yang, N. Dai, Z. Liu, Z. Jiang, J. Peng, H. Li, J. Li, M. Yamashita, and T. Akai, “Tailoring of clusters of active ions in sintered nanoporous silica glass for white light luminescence,” J. Mater. Chem. (2011).

,7

7. L. Huang, X. Wang, H. Lin, and X. Liu, “Luminescence properties of Ce3+ and Tb3+ doped rare earth borate glasses,” J. Alloy. Comp. 316(1-2), 256–259 (2001). [CrossRef]

,11

11. J. C. Zhang, C. Parent, G. Le Flem, and P. Hagenmuller, “White light emitting glasses,” J. Solid State Chem. 93(1), 17–29 (1991). [CrossRef]

]. It is shown that there is only a strong excitation band from 250nm to 350nm centered at 340nm due to the 4f→5d transition of Ce3+ ions. As for the Tb3+ single doped borosilicate glass (2b), there are several emission peaks centered at 415nm, 438nm and 457nm which is corresponding to the 5D37FJ (J = 5, 4 and 3) transition of Tb3+ ions, and there are also lots of narrow emission peaks at 490nm, 546nm, 588nm, and 624nm due to the 5D47FJ (J = 6, 5, 4 and 3) transitions of Tb3+ ions. The 5D4 emission provides strong green fluorescence. For the excitation spectrum of Tb3+-doped sample, it is indicated that there are several narrow excitation bands centered at 241, 280 and 313 nm and a broad excitation band centered at 373 nm by monitoring the 548 nm emission [2

2. Z. Liu, N. Dai, H. Luan, Y. Sheng, J. Peng, Z. Jiang, H. Li, L. Yang, and J. Li, “Enhanced green luminescence in Ce-Tb-Ca codoped sintered porous glass,” Opt. Express 18(20), 21138–21146 (2010). [CrossRef] [PubMed]

, 8

8. R. Martínez-Martínez, A. Speghini, M. Bettinelli, C. Falcony, and U. Caldiño, “White light generation through the zinc metaphosphate glass activated by Ce3+, Tb3+ and Mn2+ ions,” J. Lumin. 129(11), 1276–1280 (2009). [CrossRef]

, 11

11. J. C. Zhang, C. Parent, G. Le Flem, and P. Hagenmuller, “White light emitting glasses,” J. Solid State Chem. 93(1), 17–29 (1991). [CrossRef]

]. For the Mn2+ single doped borosilicate glass (2c), there is only a broad red emission band from 500nm to 700nm centered at 607nm, and there are several excitation bands centered at 280, 309, 355, 416 and 491 nm with a monitoring wavelength at 607 nm. The emission band of Mn2+- doped borosilicate glass can be associated with the 4T16A1 transition and the excitation bands can be assigned to the transitions from the ground state 6A1 to higher levels of Mn2+ ions [6

6. L. Yang, N. Dai, Z. Liu, Z. Jiang, J. Peng, H. Li, J. Li, M. Yamashita, and T. Akai, “Tailoring of clusters of active ions in sintered nanoporous silica glass for white light luminescence,” J. Mater. Chem. (2011).

, 8

8. R. Martínez-Martínez, A. Speghini, M. Bettinelli, C. Falcony, and U. Caldiño, “White light generation through the zinc metaphosphate glass activated by Ce3+, Tb3+ and Mn2+ ions,” J. Lumin. 129(11), 1276–1280 (2009). [CrossRef]

, 11

11. J. C. Zhang, C. Parent, G. Le Flem, and P. Hagenmuller, “White light emitting glasses,” J. Solid State Chem. 93(1), 17–29 (1991). [CrossRef]

]. It is shown that the Mn2+ has weak excitation bands in long wavelength ultraviolet region, and cannot be efficiently excited by long wavelength UV light sources. Figure 2d shows that there is a spectral overlap between the emission spectrum of Ce3+ and the excitation spectrum of Tb3+. There is also a spectral overlap between the emission spectrum of Ce3+ and the excitation spectrum of Mn2+. According to Dexter’s theory for energy transfer, there is energy transfer probability between Ce3+ and Tb3+, and also between Ce3+ and Mn2+ by nonradiative energy transfer associated with resonance between donor (Ce3+) and acceptors (Tb3+ and Mn2+) [6

6. L. Yang, N. Dai, Z. Liu, Z. Jiang, J. Peng, H. Li, J. Li, M. Yamashita, and T. Akai, “Tailoring of clusters of active ions in sintered nanoporous silica glass for white light luminescence,” J. Mater. Chem. (2011).

, 11

11. J. C. Zhang, C. Parent, G. Le Flem, and P. Hagenmuller, “White light emitting glasses,” J. Solid State Chem. 93(1), 17–29 (1991). [CrossRef]

, 13

13. D. L. Dexter, “Possibility of luminescent quantum yields greater than unity,” Phys. Rev. 108(3), 630–633 (1957). [CrossRef]

]. It is shown from Fig. 2 that the Ce3+, Tb3+ and Mn2+ are blue, green and red emitters, respectively. Furthermore, The Ce3+ can be efficient sensitizer to transfer energy to Tb3+ and Mn2+.

In order to improve the emission of Tb3+ and Mn2+ under the long-wavelength UV excitation, Ce3+ was introduced into the Tb3+ and Mn2+ single doped melting borosilicate glasses [11

11. J. C. Zhang, C. Parent, G. Le Flem, and P. Hagenmuller, “White light emitting glasses,” J. Solid State Chem. 93(1), 17–29 (1991). [CrossRef]

]. Figure 3
Fig. 3 Emission spectra (black) and excitation spectra (red) of Ce3+-Tb3+ co-doped (3a) and Ce3+-Mn2+ co-doped (3c) melting borosilicate glasses. Emission spectra of Tb3+ single doped (red) and Ce3+-Tb3+ co-doped (3b) and Mn2+ single doped (red) and Ce3+-Mn2+ co-doped (3d) melting borosilicate glasses. The excitation wavelength is 346nm for all the glasses, and the monitoring wavelengths are 547nm and 604nm for the co-doped glasses, respectively. The Ce3+-Tb3+ co-doped glass has a Ce3+ concentration of 0.8 mol% and a Tb3+ concentration of 0.8 mol%. The Ce3+-Mn2+ co-doped glass has a Ce3+ concentration of 0.8 mol% and a Mn2+ concentration of 1.5 mol%.
shows the emission spectra (black) and excitation spectra (red) of Ce3+-Tb3+ co-doped (3a) and Ce3+-Mn2+ co-doped (3c) melting borosilicate glasses and the emission spectra of single doped (red) and co-doped (black) samples (3b, 3d) under the 346nm excitation. For the Ce3+-Tb3+ co-doped melting borosilicate glass (3a), the excitation and monitoring wavelengths are 346nm and 547 nm. There is a broad emission band about 400nm and several narrow peaks centered at 491, 547, 589 and 624nm. The broad emission band and narrow emission peaks are assigned to the 5d→4f transition of Ce3+ and 5D47FJ (J = 6, 5, 4 and 3) transitions of Tb3+, respectively. Moreover, as for the excitation spectrum, there is a broad excitation band centered at 330nm due to 4f→5d transition of Ce3+. It is shown from Fig. 3b that the emission of Tb3+ is in the Ce3+-Tb3+ co-doped glass is approximately twice than that in the Tb3+ single doped glass due to the energy transfer from Ce3+ to Tb3+ [2

2. Z. Liu, N. Dai, H. Luan, Y. Sheng, J. Peng, Z. Jiang, H. Li, L. Yang, and J. Li, “Enhanced green luminescence in Ce-Tb-Ca codoped sintered porous glass,” Opt. Express 18(20), 21138–21146 (2010). [CrossRef] [PubMed]

, 6

6. L. Yang, N. Dai, Z. Liu, Z. Jiang, J. Peng, H. Li, J. Li, M. Yamashita, and T. Akai, “Tailoring of clusters of active ions in sintered nanoporous silica glass for white light luminescence,” J. Mater. Chem. (2011).

, 7

7. L. Huang, X. Wang, H. Lin, and X. Liu, “Luminescence properties of Ce3+ and Tb3+ doped rare earth borate glasses,” J. Alloy. Comp. 316(1-2), 256–259 (2001). [CrossRef]

, 11

11. J. C. Zhang, C. Parent, G. Le Flem, and P. Hagenmuller, “White light emitting glasses,” J. Solid State Chem. 93(1), 17–29 (1991). [CrossRef]

]. As for the Ce3+-Mn2+ co-doped melting borosilicate glass (3c), there are broad emission bands around 400nm and 604nm. The former is due to the 5d→4f transition of Ce3+ and the latter is due to 4T16A1 transition of Mn2+. The excitation spectrum consists of a strong band near 319nm and a weak band at 416nm with the monitoring wavelength at 604nm [6

6. L. Yang, N. Dai, Z. Liu, Z. Jiang, J. Peng, H. Li, J. Li, M. Yamashita, and T. Akai, “Tailoring of clusters of active ions in sintered nanoporous silica glass for white light luminescence,” J. Mater. Chem. (2011).

, 8

8. R. Martínez-Martínez, A. Speghini, M. Bettinelli, C. Falcony, and U. Caldiño, “White light generation through the zinc metaphosphate glass activated by Ce3+, Tb3+ and Mn2+ ions,” J. Lumin. 129(11), 1276–1280 (2009). [CrossRef]

, 11

11. J. C. Zhang, C. Parent, G. Le Flem, and P. Hagenmuller, “White light emitting glasses,” J. Solid State Chem. 93(1), 17–29 (1991). [CrossRef]

]. It is amazing that compared with the Mn2+ single doped glass, the Mn2+ ions in the Ce3+-Mn2+ co-doped glass have stronger emission whose intensity is enhanced at least eight times than that in single doped glass under the excitation of 346nm. It is shown that the emission of Mn2+ is remarkably improved due to the energy transfer from Ce3+.

The decay curves of Ce3+ emission at 395nm are examined for the samples with and without the co-doped Tb3+ and Mn2+. Figure 4
Fig. 4 Decay curves of Ce3+ emission at 395nm in the single doped and co-doped melting borosilicate glasses under 310nm excitation. Sample a is the Ce3+ single doped glass with the concentration of 0.8 mol%. Sample b is the Ce3+-Tb3+ co-doped glass with the concentration of 0.8 mol% Ce3+ and 0.8 mol% Tb3+. Sample c is the Ce3+-Mn2+ co-doped glass with the concentration of 0.8 mol% Ce3+ and 1.5 mol% Mn2+. The red lines are fitted lines of decay curves corresponding to sample a, b, and c, respectively.
presents the decay curves of Ce3+ ions emission for these samples. It can be seen from Fig. 4 that the decay curves of Ce3+ ions are well fitted with a second order exponenitial equation: I(t) = I(0) + Aexp(-t/τ1) + Bexp (-t/τ2) where I0 and I are the luminescence intensity initially and at t, A and B are constants and τ1 and τ2 are lifetimes. In the absence of Tb3+ and Mn2+ ions, the lifetime of Ce3+ ions is 46.2ns. With the co-doped Tb3+ and Mn2+ ions, the lifetime of Ce3+ ions have decreased to 44.4ns and 40.4ns, respectively. These phenomena indicate that the excitation energy of Ce3+ ions is transferred to Tb3+ and Mn2+ ions.

Because the pure emission colors, the Ce-Tb-Mn co-doped glasses will be good candidates for white light emitting glasses. To obtain the optimal white light emitting, we prepared some samples by adjusting the concentration of different co-dopants. Figure 5
Fig. 5 Emission spectra of Ce3+-Tb3+-Mn2+ co-doped melting borosilicate glasses under 346nm excitation. Sample 5a has a Ce3+ concentration of 0.8 mol%, a Tb3+ concentration of 0.6 mol% and a Mn2+ concentration of 1.5 mol%. Sample 5b has a Ce3+ concentration of 0.8 mol%, a Tb3+ concentration of 0.8 mol% and a Mn2+ concentration of 1.5 mol%. Sample 5c has a Ce3+ concentration of 0.8 mol%, a Tb3+ concentration of 0.8 mol% and a Mn2+ concentration of 1.6 mol%. The CIE (X, Y) coordinate diagram shows the chromaticity points of sample 5a (1), sample 5b (2) and sample 5c (3), respectively. The inset shows the fluorescence photographs of white-emitting of sample 5a, 5b and 5c under 346nm UV lamp irradiation.
exhibits the emission spectra of Ce3+-Tb3+-Mn2+ co-doped glasses. The sample 5a has the same concentration of Ce3+ and Mn2+ with sample 5b and they have different Tb3+ concentration of 0.6 and 0.8 mol%, respectively. Simple 5c has the same concentration of Ce3+ and Tb3+ with the sample 5b and they have different Mn2+ concentration of 1.6 and 1.5 mol%, respectively. It is shown that there are blue, green and red emissions under 346nm excitation. It can be seen that the blue emission of the cerium decreases as the concentration of terbium and manganese increased. This can be ascribed to the energy transfer from Ce3+ to Tb3+ and Mn2+, the more concentration of Tb3+ and Mn2+, the more Ce3+ emission would be suppressed and facilitated the Tb3+ and Mn2+ emission. The blue emission of the terbium increases as the concentration of terbium increased, while decreases as the concentration of manganese increased. The red emission of the manganese decreases as the concentration of terbium and manganese increased. The former can be ascribed to the energy transfer from the Ce3+ to Tb3+, and the latter can be ascribed to the clustering of manganese ions. To further understand the white light emission of these samples in Fig. 5, we calculate their color coordinates according to the standard of CIE 1931, which has been characterized by CIE chromaticity diagram. And we also calculated the correlated color temperature (CCT) and color rendering index (CRI) of the co-doped glasses by the method discussed in the publicly available CIE 13.3-1995. The chromaticity varies with the change of the activator concentrations. The chromaticity points of sample 5a (x = 0.313, y = 0.292; CCT = 6807K, Ra = 82.9), sample 5b (x = 0.318, y = 0.333; CCT = 6202K, CRI = 72.5) and sample 5c (x = 0.308, y = 0.325; CCT = 6805K, CRI = 67.6) have been marked by the asterisks respectively in Fig. 5. All points mentioned above are located within the elliptic region which is the white light emitting region. It demonstrates that the color coordinate of simple 5b is very close to the ideal white light. Although simple 5a has a higher CRI of 82.9 and lower CCT of 6807K compared with a white LED fabricated using YAG: Ce3+ phosphor pumped with a blue InGaN chip, the CRI and CCT of the samples in Fig. 5 are generally low. In the follow-up experiments, we will make effects to increase the color rendering index and decrease the correlated color temperature of the Ce-Tb-Mn co-doped melting borosilicate glasses.

4. Conclusions

In conclusion, the melting borosilicate glasses co-doped with Ce3+, Tb3+ and Mn2+ ions were successfully prepared. The color coordinate, the correlated color temperature and the color rendering index were calculated to manifest the color properties of these glasses. The color coordinate (x = 0.318, y = 0.333) is very close to ideal white light under long wavelength ultraviolet excitation. The energy transfer of these Ce3+-Tb3+-Mn2+ co-doped borosilicate glasses have been studied. Due to their ideal white light under long wavelength ultraviolet excitation, the Ce3+-Tb3+-Mn2+ co-doped glasses have a potential for application in optical fibers, LED displays and fluorescent lamps.

Acknowledgments

This work was supported by the National High-Technology Research and Development Program of China (2011AA030201) and Fundamental Research Funds for the Central Universities (HUST: NO. 2010QN053). The authors would like to thank the Hubei Optoelectronics Testing Center and Huazhong University of Science and Technology Analytical and Testing Center for sharing their equipments.

References and links

1.

M. Jayasimhadri, K. Jang, H. S. Lee, B. Chen, S. S. Yi, and J. H. Jeong, “White light generation from Dy3+-doped ZnO–B2O3–P2O5 glasses,” J. Appl. Phys. 106(1), 13105 (2009). [CrossRef]

2.

Z. Liu, N. Dai, H. Luan, Y. Sheng, J. Peng, Z. Jiang, H. Li, L. Yang, and J. Li, “Enhanced green luminescence in Ce-Tb-Ca codoped sintered porous glass,” Opt. Express 18(20), 21138–21146 (2010). [CrossRef] [PubMed]

3.

J. Wang, Z. Zhang, M. Zhang, Q. Zhang, Q. Su, and J. Tang, “The energy transfer from Eu2+ to Tb3+ in Ca10K (PO4) 7 and its application in green light emitting diode,” J. Alloy. Comp. 488(2), 582–585 (2009). [CrossRef]

4.

J. S. Kim, P. E. Jeon, Y. H. Park, J. C. Choi, H. L. Park, G. C. Kim, and T. W. Kim, “White-light generation through ultraviolet-emitting diode and white-emitting phosphor,” Appl. Phys. Lett. 85(17), 3696–3698 (2004). [CrossRef]

5.

M. Peng and L. Wondraczek, “Orange‐to‐Red Emission from Bi2+ and Alkaline Earth Codoped Strontium Borate Phosphors for White Light Emitting Diodes,” J. Am. Ceram. Soc. 93, 1437–1442 (2010).

6.

L. Yang, N. Dai, Z. Liu, Z. Jiang, J. Peng, H. Li, J. Li, M. Yamashita, and T. Akai, “Tailoring of clusters of active ions in sintered nanoporous silica glass for white light luminescence,” J. Mater. Chem. (2011).

7.

L. Huang, X. Wang, H. Lin, and X. Liu, “Luminescence properties of Ce3+ and Tb3+ doped rare earth borate glasses,” J. Alloy. Comp. 316(1-2), 256–259 (2001). [CrossRef]

8.

R. Martínez-Martínez, A. Speghini, M. Bettinelli, C. Falcony, and U. Caldiño, “White light generation through the zinc metaphosphate glass activated by Ce3+, Tb3+ and Mn2+ ions,” J. Lumin. 129(11), 1276–1280 (2009). [CrossRef]

9.

L. Yang, M. Yamashita, and T. Akai, “Green and red high-silica luminous glass suitable for near-ultraviolet excitation,” Opt. Express 17(8), 6688–6695 (2009). [CrossRef] [PubMed]

10.

S. Liu, G. Zhao, X. Lin, H. Ying, J. Liu, J. Wang, and G. Han, “White luminescence of Tm-Dy ions co-doped aluminoborosilicate glasses under UV light excitation,” J. Solid State Chem. 181(10), 2725–2730 (2008). [CrossRef]

11.

J. C. Zhang, C. Parent, G. Le Flem, and P. Hagenmuller, “White light emitting glasses,” J. Solid State Chem. 93(1), 17–29 (1991). [CrossRef]

12.

T. Tsuboi, “Optical properties of Ce3+/Tb3+-codoped borosilicate glass,” EPJ Appl. Phys. (Berl.) 26, 95–101 (2004). [CrossRef]

13.

D. L. Dexter, “Possibility of luminescent quantum yields greater than unity,” Phys. Rev. 108(3), 630–633 (1957). [CrossRef]

OCIS Codes
(160.2750) Materials : Glass and other amorphous materials
(160.5690) Materials : Rare-earth-doped materials
(250.5230) Optoelectronics : Photoluminescence

ToC Category:
Materials

History
Original Manuscript: July 5, 2011
Revised Manuscript: August 7, 2011
Manuscript Accepted: August 7, 2011
Published: September 22, 2011

Citation
Yang Yu, Zijun Liu, Nengli Dai, Yubang Sheng, Huaixun Luan, Jinggang Peng, Zuowen Jiang, Haiqing Li, Jinyan Li, and Luyun Yang, "Ce-Tb-Mn co-doped white light emitting glasses suitable for long-wavelength UV excitation," Opt. Express 19, 19473-19479 (2011)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-19-20-19473


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References

  1. M. Jayasimhadri, K. Jang, H. S. Lee, B. Chen, S. S. Yi, and J. H. Jeong, “White light generation from Dy3+-doped ZnO–B2O3–P2O5 glasses,” J. Appl. Phys.106(1), 13105 (2009). [CrossRef]
  2. Z. Liu, N. Dai, H. Luan, Y. Sheng, J. Peng, Z. Jiang, H. Li, L. Yang, and J. Li, “Enhanced green luminescence in Ce-Tb-Ca codoped sintered porous glass,” Opt. Express18(20), 21138–21146 (2010). [CrossRef] [PubMed]
  3. J. Wang, Z. Zhang, M. Zhang, Q. Zhang, Q. Su, and J. Tang, “The energy transfer from Eu2+ to Tb3+ in Ca10K (PO4) 7 and its application in green light emitting diode,” J. Alloy. Comp.488(2), 582–585 (2009). [CrossRef]
  4. J. S. Kim, P. E. Jeon, Y. H. Park, J. C. Choi, H. L. Park, G. C. Kim, and T. W. Kim, “White-light generation through ultraviolet-emitting diode and white-emitting phosphor,” Appl. Phys. Lett.85(17), 3696–3698 (2004). [CrossRef]
  5. M. Peng and L. Wondraczek, “Orange‐to‐Red Emission from Bi2+ and Alkaline Earth Codoped Strontium Borate Phosphors for White Light Emitting Diodes,” J. Am. Ceram. Soc.93, 1437–1442 (2010).
  6. L. Yang, N. Dai, Z. Liu, Z. Jiang, J. Peng, H. Li, J. Li, M. Yamashita, and T. Akai, “Tailoring of clusters of active ions in sintered nanoporous silica glass for white light luminescence,” J. Mater. Chem. (2011).
  7. L. Huang, X. Wang, H. Lin, and X. Liu, “Luminescence properties of Ce3+ and Tb3+ doped rare earth borate glasses,” J. Alloy. Comp.316(1-2), 256–259 (2001). [CrossRef]
  8. R. Martínez-Martínez, A. Speghini, M. Bettinelli, C. Falcony, and U. Caldiño, “White light generation through the zinc metaphosphate glass activated by Ce3+, Tb3+ and Mn2+ ions,” J. Lumin.129(11), 1276–1280 (2009). [CrossRef]
  9. L. Yang, M. Yamashita, and T. Akai, “Green and red high-silica luminous glass suitable for near-ultraviolet excitation,” Opt. Express17(8), 6688–6695 (2009). [CrossRef] [PubMed]
  10. S. Liu, G. Zhao, X. Lin, H. Ying, J. Liu, J. Wang, and G. Han, “White luminescence of Tm-Dy ions co-doped aluminoborosilicate glasses under UV light excitation,” J. Solid State Chem.181(10), 2725–2730 (2008). [CrossRef]
  11. J. C. Zhang, C. Parent, G. Le Flem, and P. Hagenmuller, “White light emitting glasses,” J. Solid State Chem.93(1), 17–29 (1991). [CrossRef]
  12. T. Tsuboi, “Optical properties of Ce3+/Tb3+-codoped borosilicate glass,” EPJ Appl. Phys. (Berl.)26, 95–101 (2004). [CrossRef]
  13. D. L. Dexter, “Possibility of luminescent quantum yields greater than unity,” Phys. Rev.108(3), 630–633 (1957). [CrossRef]

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