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Journal of Luminescence 126 (2007) 707–710

Rare earth ions doped full-color luminescence glasses for white LED
Chaofeng Zhu, Yunxia Yang, Xiaoluan Liang, Shuanglong Yuan, Guorong ChenÃ
Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, PR China Received 20 July 2006; received in revised form 23 October 2006; accepted 31 October 2006 Available online 8 December 2006

Abstract Silicate and phosphate glasses co-doped with rare-earth ions (REIs)(Ce3+, Tb3+, Eu3+) are presented in the present work. Their photoluminescence properties were studied by excitation and emission spectra. A combination of blue, green and red bands is shown for both silicate and phosphate glasses that allows the observation of white light when the glass is excited by UV light. The relative emission intensity ratios of the green to the red can be tuned by varying the concentrations of activator and/or sensitizer as well as the composition of glass matrices. r 2006 Elsevier B.V. All rights reserved.
Keywords: W-LED; Luminescence; Glass; Rare-earth ion

1. Introduction Rare-earth ions (REI) possess unique optical behavior when doped into materials and have paved the way for the development of phosphors for different applications. In recent years, studies on REI-doped glasses have gained much interest of researchers for the reason that the particular 4f electronic configuration of REI in varied glass matrixes leads to emissions from ultraviolet to infrared [1,2] with many potential uses including fluorescent lamps, two-dimensional X-ray sensors, solar control devices, solid laser and optical amplifiers, etc. [3–5]. Nowadays, white light-emitting-diodes (W-LEDs) have emerged as an important class of lighting devices and show high potential for replacement of conventional lighting sources like incandescent and fluorescent lamps, the advantage being their long lifetime, lower energy consumption, higher reliability and environmental-friendly characteristics [6]. At present, W-LED is realized by using two or three kinds of phosphors or a kind of full color phosphor excited by the UV LED chip [7]. Luminescence glass has some advantages compared to phosphors when used in the preparation of W-LED, such
ÃCorresponding author. Tel: +86 21 64247463.

as lower production cost, simpler manufacture procedure, free of halo effect, etc. Thus, we think it is feasible that luminescence glass can be used to replace phosphors for W-LED, which, to the author’s knowledge, has been scarcely reported. In the present work, the novel full-color luminescence glasses based on silicate and phosphate systems are studied, following the requirements of W-LED, that is, well absorbing the UV light of InGaN-based LED chip and converting it into white light. Besides, the dependence of luminescence property on the concentrations of REI activators and glass matrix compositions are examined in this paper. 2. Experimental The glass samples used in this paper are based on silicate and phosphate systems. To realize the full-color luminescence, Eu3+, Tb3+ and/or Ce3+ ions are co-doped as the activators. The nominal compositions of all glass samples are listed in Table 1. The glass samples were prepared from melts of high-purity grade of oxides or salts including NH4H2PO4, H3BO3, CaCO3, BaCO3, SrCO3, SiO2, Eu2O3, Tb4O7 and Ce(NO3)3 Á 6H2O. Calculated amounts of the starting materials were taken in an agate mortar and powdered well to obtain homogenous mixtures. The

E-mail address: (G. Chen). 0022-2313/$ - see front matter r 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.jlumin.2006.10.028

708 Table 1 Composition of analyzed glasses (mol %) Glass no. SCB-1 SCB-2 SCB-3 SCB-4 PSB-1 PSB-2 PSB-3 P2O5 SiO2 50 50 45 40 60 60 60 20 20 20 SrO CaO 37 37 37 37 BaO 13 13 13 13 15 15 15 B2O3 Ce2O3 0.25 0.25 0.25 0.25 1 1 Tb2O3 0.125 0.125 0.125 0.125 0.5 0.5 0.5 Eu2O3 0.5 0.75 0.75 0.75 0.5 0.5 1 C. Zhu et al. / Journal of Luminescence 126 (2007) 707–710

5 10 5 5 5

well-mixed batches were put into alumina crucibles and melted in an electrical furnace at 1250 1C for phosphate glass or 1500 1C for silicate glass for 2 h. To avoid oxidation of Ce3+ and Tb3+ ions during melting, a weak reducing atmosphere was applied by using carbon granules and nitrogen. The melts were then quickly poured into a preheated stainless steel mold for quenching in air. To obtain thermal and structural stability, the glass samples were annealed at a temperature of 450 1C (phosphate glass) or 500 1C (silicate glass) for 2 h. To investigate the luminescence properties of the glasses, the excitation and emission spectra were recorded on a Fluorolog-3-P fluorescent spectrometer, using Xenon lamp as the excitation source. All measurements were performed at room temperature and with the same instrument parameters. 3. Results and discussion

1.0 0.9 0.8 0.7 Intensity(a.u.) 0.6 0.5 0.4 0.3 0.2 0.1 0.0 350 400 450 500 550 600 Wavelength(nm) 650 700 750 SCB-1 SCB-2

Fig. 1. Emission spectra for sample SCB-1 and SCB-2 excited by 376 nm.

Fig. 1 shows the emission spectra of sample SCB-1 and SCB-2 upon excitation with a light of 376 nm. This kind of glass samples activated by Ce3+, Tb3+ and Eu3+ ions exhibit simultaneously the blue (488 nm), green (542 nm) and red (611 nm) emissions. The broad blue emission is aroused from the 5d–4f transitions of Ce3+ ions, which in solids are parity-allowed electric dipole transitions and have large oscillator strength, thus producing efficient broadband luminescence [1]. The green and red emissions, on the other hand, are ascribed to 5D4–7F5 transitions of Tb3+ ions [8] and the 5D0–7F2 transitions of Eu3+ ions [4], respectively. It is worth noticing that the emission intensity ratio of the red (611 nm) to the green (542 nm) changes from 0.496 (the sample SCB-1) to 0.678 (the sample SCB-2), indicating that chromaticity parameters of glass can be tuned by changing the respective rates of the activators. This is very important for lighting applications because the global emission should be characterized by its chromaticity coordinates in the CIE chromaticity diagram [9]. The emission spectra for samples SCB-3 and SCB-4 at 376 nm excitation source are given in Fig. 2, where the emission spectrum of the sample SCB-2 is also included for comparison. It can be seen from Table 1 that glasses SCB-3 and SCB-4 have the same compositions as the glass SCB-2 except partial substitution of B2O3 for SiO2. As shown in Fig. 2, such a difference does not change the shape and the








0.0 350 400 450 500 550 600 650 700 750


Fig. 2. Emission spectra for sample SCB-2, SCB-3 and SCB-4 excited by 376 nm.

position of emission lines but plays a role in adjusting the intensity ratio of respective emission peaks. If the intensity of green emission (542 nm) is considered as a unit, the emission intensity ratios of the blue (488 nm) and the red (611 nm) to the green are 0.996 and 0.681 for the B2O3-free sample (SCB-2), which change to 1.005, 0.619 and 1.141, 0.472 for the B2O3-containing samples (SCB-3 and SCB-4). That is, with increased B2O3 by replacing SiO2 on the same

C. Zhu et al. / Journal of Luminescence 126 (2007) 707–710 709

basis, the blue emission becomes more enhanced at the cost of the red emission. This phenomenon indicates the dependence of the intensity of emission lines not only on the concentration of activators but also on the composition of glass matrix. This is not unusual because the luminescence behavior of REI is generally influenced by the chemical environment surrounding them as many previously reported works demonstrated [10]. In the present work, the increased covalent degree of oxygen bonding with glass network former cations due to introduction of the higher covalent B3+ is most likely the reason. Since the 5d–4f transition of Ce3+ ions is sensitive to the ligand field at its site and enhanced by the increased covalency of oxygen bond, the blue emission of the present samples therefore becomes stronger with increasing B2O3 content. Excitation spectra of SCB group glasses exhibit similar characteristics. As an example, Fig. 3 shows the excitation spectra of the sample SCB-1 monitored at 488, 542 and 611 nm, respectively. Efficient excitation with UV radiation is confirmed in the figure. In particular, excitation spectra monitored at 488 and 542 nm present broad and almost overlapped bands that are due to the 4f–5d electronic transitions of Ce3+ ions, and the transitions from the ground level 7F6 to 5D2 of Tb3+ ions. On the other hand, the spectrum monitored at 611 nm consists of four bands peaking at $361,380,392 and 413 nm and they correspond to the electronic transitions of Eu3+ ions from ground state 7 F0 to excited states 5D4 (361 nm), 5G3(380 nm), 5 L6(392 nm) and 5D3(413 nm), respectively [11,12]. It is noticed from analysis in Fig. 3 that the broad excitation bands from Ce3+ and Tb3+ ions and the sharp excitation bands due to Eu3+ ions cover coincidently the wavelength region from 350 to 400 nm, which nicely fits the requirements of W-LED. Fig. 4 shows the emission spectra for phosphate glass samples excited at 376 nm where the emission lines attributed to Tb3+ and Eu3+ are observed. The Tb3+ emission bands include those peaking at 412, 435, 486 and


0.8 PSB-3 Intensity(a.u.) 0.6 PSB-2 PSB-1



0.0 400 425 450 475 500 525 550 575 600 625 650 675 Wavelength(nm)
Fig. 4. Emission spectra excited by 376 nm for sample PSB-1, PSB-2 and PSB-3, respectively.

0.8 Intensity(a.u.)



0.4 542nm 488nm


0.0 250 300 350 400 Wavelength(nm) 450 500

Fig. 3. Excitation spectra for sample SCB-1 monitored at 488, 542 and 611 nm, respectively.

542 nm and they are assigned to the transitions of 5D3–7F5, 5 D3–7F4, 5D4–7F6, and 5D4–7F5electrical levels, respectively [13]. Besides, the emission band corresponding to the transitions of 5D4–7F5 splits into two peaks whereas for SCB group glasses only a shoulder is observed aside. This phenomenon indicates that phosphate glass network has a higher distortion effect than its counterpart silicate glass network on Tb3+ ions leading to the larger Stark split of energy level. Eu3+ emissions situate at 591, 611 and 652 nm and are attributed to the 5D0–7FJ (J ¼ 1; 2; 3) transitions [4,14]. It is reported that the emission band of Ce3+ ions in phosphate glass is in the range of UV because of the lower optical basicity of glass matrix compared with the silicate glass [15]. Hence, the samples PSB-2 and PSB-3 containing Ce3+ ions do not display Ce3+ emission bands. Although the shape and position of the emission bands for these three samples are identical, the emission intensity of samples PSB-2 is enhanced, indicating that Ce3+ ions act as sensitizers on the luminescence of the Tb3+ and Eu3+ ions. As mentioned above, Ce3+ emissions in phosphate glass matrix locate in the UV region overlapping coincidentally the excitation wavelengths of Tb3+ and Eu3+ and this is just the basis of sensitization effect due to the efficient energy transfer from Ce3+ ions (sensitizers) to Tb3+ ions and Eu3+ ions (activators). The emission spectral comparison between these three samples also shows that the emission intensity ratio of the red (611 nm) to the green (542 nm) is dependent not only on the concentration of activator Eu3+ but also on that of sensitizer Ce3+. Namely, an increase in Eu3+ content from 1 to 2 mol% leads to change of the ratio from 1.67 to 2.28, while the introduction of Ce3+ results in an increase of the ratio from 1.62 to 1.67. This is interesting and essential for the purpose of W-LED applications because the easier adjustment of the light tune becomes possible. Fig. 5 shows the excitation spectra of phosphate glass (PSB-2) monitored at 611 and 542 nm, respectively. In the former case, four excitation bands are observed and they

710 C. Zhu et al. / Journal of Luminescence 126 (2007) 707–710

1.0 542nm 611nm

0.8 Intensity(a.u.)




0.0 345

the white light emission under UV light from the InGaNbased UV chip. In addition, sensitizing effect of Ce3+ ions to the luminescence of Tb3+ and Eu3+ ions is observed in phosphate glasses due to the overlapping of emissions from Ce3+ with the excitation bands of activators. For silicate glasses, the intensity ratio of the red to green emissions can be tuned by varying the concentrations of Eu3+ ions and glass matrix composition. Whereas for phosphate glasses both activator (Eu3+) and sensitizer (Ce3+) contribute to the adjustment of the emission intensity ratio. Silicate glasses are more favorable due to availability of a broad excitation band covering the wavelength region from 350 to 400 nm, thus, more effective for developing W-LED.
435 450



390 405 420 Wavelength(nm)

[1] P.I. Paulose, G. Jose, V. Thomas, et al., J. Phys. Chem. Solids 64 (2003) 841. [2] M. Nogami, T. Enomoto, T. Hayakawa, J. Lumin. 97 (2002) 147. [3] S.E. Paje, M.A. Garcia, M.A. Villegas, et al., Opt. Mater. 17 (2001) 459. [4] Y.P. Reddy, S. Buddhudu, N.S. Hussain, Mater. Res. Bull. 36 (2001) 1813. [5] Y. Lin, Z. Tang, Z. Zhang, J. Zhang, et al., Mater. Sci. Eng. B 86 (2001) 79. [6] C. Zhu, Y. Yang, G. Chen, et al., in: Proceedings of the Ninth International Conference on Particle Physics, October 2005, Como, Italy. [7] J.S. Kim, K.T. Lim, Y. Jeong, et al., Solid State Commun. 135 (2005) 21. [8] J. Zhao, C. Li, S. Wang, et al., Chin. J. Lumin. 6 (2004) 655. [9] N.E. Jouhari, C. Parent, G.L. Flem, J. Solid State Chem. 123 (1996) 398. [10] T. Kim, Y. Yoon, D. Kil, et al., Mater. Lett. 47 (2001) 290. [11] M. Wang, X. Fan, G. Xiong, J. Phys. Chem. Solids 56 (1995) 859. [12] M. Nogami, T. Yamazaki, Y. Abe, J. Lumin. 78 (1998) 63. [13] J. Chen, C. Zu, J. Chen, et al., J. Func. Mater. 10 (2001) 149 (in Chinese). [14] V. Aruna, N.S. Hussain, K. Annapurna, et al., Mater. Lett. 33 (1997) 201. [15] C. Jiang, Q. Zeng, H. Liu, et al., J. Funct. Mater. 2 (2001) 198 (in Chinese). [16] L. Hai, E.Y. Pun, X. Wang, et al., J. Alloys Compds. 390 (2005) 197.

Fig. 5. Excitation spectra for sample PSB-2 monitored at 542 and 611 nm, respectively.

peak at the same positions as silicate glasses (SCB group) corresponding to the electronic transitions from Eu3+ ions. In the latter case, however, the fine excitation band structure of Tb3+ ions appears, which consists of four excitation bands peaking at 350, 356, 368 and 376 nm, respectively. These bands are [16] associated with the transitions from the ground state 7F6 to 5D2, 5D3 and 5D4 and other higher 4f excited levels, respectively. They also lie in the UV region, but do not present the broad band, thus being less satisfactory to be used in the fabrication of W-LED. 4. Conclusions In summary, silicate and phosphate glasses co-doped with Ce3+, Tb3+ and Eu3+ ions were successfully synthesized by the melt quench method. Both silicateand phosphate-luminescence glasses can be effectively excited by UV light and exhibit a combination of the blue, green and red emissions, thus realizing the generation of