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Optics Express

Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 20, Iss. 28 — Dec. 31, 2012
  • pp: 29743–29750
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Tunable white luminescence and energy transfer in novel Cu+, Sm3+ co-doped borosilicate glasses for W-LEDs

RongFei Wei, ChongGeng Ma, YunLe Wei, JiaYu Gao, and Hai Guo  »View Author Affiliations


Optics Express, Vol. 20, Issue 28, pp. 29743-29750 (2012)
http://dx.doi.org/10.1364/OE.20.029743


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Abstract

The luminescent properties of novel Cu+, Sm3+ single- and co-doped borosilicate glasses were systematically investigated by absorption, excitation, emission spectra and decay curves. Cu+ single-doped glasses emit broad luminescence band covering all the visible range. And their peaks shift to blue with decreasing excitation wavelength from 330 to 280 nm. Cu+, Sm3+ co-doped samples generate the varied hues from blue white to pure white and eventually to yellow white due to an efficient energy transfer from Cu+ to Sm3+. Our research indicates the potential application of Cu+, Sm3+ co-doped borosilicate glasses as converting phosphors for white LEDs pumped by UV LED chips.

© 2012 OSA

1. Introduction

Recently, W-LEDs fabricated by ultraviolet (UV) LED chip coupled with tri-color phosphors have been investigated extensively due to the remarkable development of UV diodes. However, the efficiency of W-LEDs developed by this method is low since the strong re-absorption of blue light by green and red phosphors [3

3. H. Guo, H. Zhang, J. J. Li, and F. Li, “Blue-white-green tunable luminescence from Ba2Gd2Si4O13:Ce3+,Tb3+ phosphors excited by ultraviolet light,” Opt. Express 18(26), 27257–27262 (2010). [CrossRef] [PubMed]

]. Therefore, it is urgent and interesting to develop novel single-phased multi-activators co-doped systems capable of emitting white light under UV chip excitation, which are based on the luminescence and energy transfer (ET) between multi-activators [7

7. N. Guo, H. P. You, Y. H. Song, M. Yang, K. Liu, Y. H. Zheng, Y. J. Huang, and H. J. Zhang, “White-light emission from a single-emitting-component Ca9Gd(PO4)7:Eu2+, Mn2+ phosphor with tunable luminescent properties for near-UV light-emitting diodes,” J. Mater. Chem. 20(41), 9061–9067 (2010). [CrossRef]

11

11. G. G. Li, D. L. Geng, M. M. Shang, C. Peng, Z. Y. Cheng, and J. Lin, “Tunable luminescence of Ce3+/Mn2+ -coactivated Ca2Gd8(SiO4)6O2 through energy transfer and modulation of excitation: potential single-phase white/yellow-emitting phosphors,” J. Mater. Chem. 21(35), 13334–13344 (2011). [CrossRef]

]. Besides, compared to conventional phosphors used for W-LEDs, luminescent glasses not only present excellent optical properties, better mechanical properties, lower production cost and simpler manufacturing procedures, but also show an epoxy-resin free assembly process [12

12. D. Chen, Y. Yu, H. Lin, P. Huang, F. Weng, Z. Shan, and Y. Wang, “CeF3-based glass ceramic: A potential luminescent host for white-light-emitting diode,” Opt. Lett. 34(19), 2882–2884 (2009). [CrossRef] [PubMed]

14

14. H. Guo, R. F. Wei, and X. Y. Liu, “Tunable white luminescence and energy transfer in (Cu+)2, Eu3+ codoped sodium silicate glasses,” Opt. Lett. 37(10), 1670–1672 (2012). [CrossRef] [PubMed]

].

Consequently, white light has been generated by doping multi-activators such as Ce3+/Mn2+ [9

9. C. H. Huang and T. M. Chen, “A novel single-composition trichromatic white-light Ca3Y(GaO)3(BO3)4:Ce3+, Mn2+, Tb3+ phosphor for UV-light emitting diodes,” J. Phys. Chem. C 115(5), 2349–2355 (2011). [CrossRef]

11

11. G. G. Li, D. L. Geng, M. M. Shang, C. Peng, Z. Y. Cheng, and J. Lin, “Tunable luminescence of Ce3+/Mn2+ -coactivated Ca2Gd8(SiO4)6O2 through energy transfer and modulation of excitation: potential single-phase white/yellow-emitting phosphors,” J. Mater. Chem. 21(35), 13334–13344 (2011). [CrossRef]

], Eu2+/Mn2+ [7

7. N. Guo, H. P. You, Y. H. Song, M. Yang, K. Liu, Y. H. Zheng, Y. J. Huang, and H. J. Zhang, “White-light emission from a single-emitting-component Ca9Gd(PO4)7:Eu2+, Mn2+ phosphor with tunable luminescent properties for near-UV light-emitting diodes,” J. Mater. Chem. 20(41), 9061–9067 (2010). [CrossRef]

, 8

8. C. H. Huang, W. R. Liu, and T. M. Chen, “Single-phased white-light phosphors Ca9Gd(PO4)7:Eu2+, Mn2+ under near-ultraviolet excitation,” J. Phys. Chem. C 114(43), 18698–18701 (2010). [CrossRef]

], Ce3+/Sm3+ [15

15. H. Yang, G. Lakshminarayana, Y. Teng, S. Zhou, and J. Qiu, “Tunable luminescence from Sm3+, Ce3+ codoped Al2O3-La2O3-SiO2 glasses for white light emission,” J. Mater. Res. 24(05), 1730–1734 (2009). [CrossRef]

] and Tb3+/Sm3+ [16

16. X. Liang, Y. Yang, C. Zhu, S. Yuan, G. Chen, A. Pring, and F. Xia, “Luminescence properties of Tb3+ - Sm3+ codoped glasses for white light emitting diodes,” Appl. Phys. Lett. 91(9), 091104 (2007). [CrossRef]

] in various powder phosphors and glasses. More interesting, the luminescent properties and ET process of noble metal species and rare earth ions (REI) co-doped glasses such as (Cu+)2/Eu3+ [14

14. H. Guo, R. F. Wei, and X. Y. Liu, “Tunable white luminescence and energy transfer in (Cu+)2, Eu3+ codoped sodium silicate glasses,” Opt. Lett. 37(10), 1670–1672 (2012). [CrossRef] [PubMed]

], Ag/Eu3+ [13

13. H. Guo, X. Wang, J. Chen, and F. Li, “Ultraviolet light induced white light emission in Ag and Eu3+ co-doped oxyfluoride glasses,” Opt. Express 18(18), 18900–18905 (2010). [CrossRef] [PubMed]

, 17

17. M. Eichelbaum and K. Rademann, “Plasmonic enhancement or energy transfer? on the luminescence of gold-, silver-, and lanthanide-doped silicate glasses and its potential for light-emitting devices,” Adv. Funct. Mater. 19(13), 2045–2052 (2009). [CrossRef]

], Au/Eu3+ [17

17. M. Eichelbaum and K. Rademann, “Plasmonic enhancement or energy transfer? on the luminescence of gold-, silver-, and lanthanide-doped silicate glasses and its potential for light-emitting devices,” Adv. Funct. Mater. 19(13), 2045–2052 (2009). [CrossRef]

], Ag/Sm3+ [17

17. M. Eichelbaum and K. Rademann, “Plasmonic enhancement or energy transfer? on the luminescence of gold-, silver-, and lanthanide-doped silicate glasses and its potential for light-emitting devices,” Adv. Funct. Mater. 19(13), 2045–2052 (2009). [CrossRef]

, 18

18. J. J. Li, R. F. Wei, X. Y. Liu, and H. Guo, “Enhanced luminescence via energy transfer from Ag+ to RE ions (Dy3+, Sm3+, Tb3+) in glasses,” Opt. Express 20(9), 10122–10127 (2012). [CrossRef] [PubMed]

] and Au/Sm3+ [17

17. M. Eichelbaum and K. Rademann, “Plasmonic enhancement or energy transfer? on the luminescence of gold-, silver-, and lanthanide-doped silicate glasses and its potential for light-emitting devices,” Adv. Funct. Mater. 19(13), 2045–2052 (2009). [CrossRef]

] co-doped systems have become an attractive subject to achieve tunable luminescence. But, to the best of our knowledge, no report has been carried out on Cu+, Sm3+ co-doped glasses.

Fluorescence of Cu+ comes from excited s state to ground d state (d9s→d10) transition, which is strictly forbidden for free ions but partially allowed in solids by electronic coupling with lattice vibrations of odd parity. Generally, the s excited state splits into singlet (1T2g, 1Eg) and triplet (3T2g, 3Eg) parts, and after that the triplets may be split further by spin-orbit interactions [14

14. H. Guo, R. F. Wei, and X. Y. Liu, “Tunable white luminescence and energy transfer in (Cu+)2, Eu3+ codoped sodium silicate glasses,” Opt. Lett. 37(10), 1670–1672 (2012). [CrossRef] [PubMed]

, 19

19. J. D. Barrie, B. Dunn, G. Hollingsworth, and J. I. Zink, “Optical spectroscopy of copper(I)-doped Na+-β″-alumina,” J. Phys. Chem. 93(10), 3958–3963 (1989). [CrossRef]

21

21. K. Fukumi, A. Chayahara, K. Ohora, N. Kitamura, Y. Horino, K. Fujii, M. Makihara, J. Hayakaya, and N. Ohno, “Photoluminescence of Cu+-doped silica glass prepared by MeV ion implantation,” Nucl. Instrum. Meth. B. 149(1-2), 77–80 (1999). [CrossRef]

]. Thus Cu+ ions exhibit broad excitation at UV band and wide emission at visible (VIS) region, which are very sensitive to host compositions. Accordingly, for Cu+, Sm3+ co-doped glasses, the ET process from Cu+ to Sm3+ can occur, and consequently the luminescence may be tuned.

In this manuscript, borosilicate glasses were selected as host materials [22

22. Y. Yu, Z. Liu, N. Dai, Y. Sheng, H. Luan, J. Peng, Z. Jiang, H. Li, J. Li, and L. Yang, “Ce-Tb-Mn co-doped white light emitting glasses suitable for long-wavelength UV excitation,” Opt. Express 19(20), 19473–19479 (2011). [CrossRef] [PubMed]

]. The luminescent properties of Cu+, Sm3+ single- and co-doped borosilicate glasses and ET process from Cu+ exhibit to Sm3+ were investigated systematically. Adjustable emissions from blue white through pure white to yellow white were obtained.

2. Experimental

The nominal host composition (in mol%) is 50SiO2-14B2O3-10Al2O3-3Na2O-8MgO-8ZnO-3.5ZrO2-3.5Gd2O3. Samples G-host (the host), GSm2 (doped with 2 SmO3/2), GCux (xCuO), GCu2Smy (2CuO and ySmO3/2) were prepared by melt-quenching method. Raw materials were first mixed homogeneously in an agate mortar by adding ethanol and dried in an oven at 120 °C for 20 min, then melted in a covered corundum crucible at 1400 °C for 1 h in air atmosphere. The melts were poured onto a 300 °C preheated stainless-steel mold and pressed by another plate, then cooled down to room temperature to form glasses. Finally, all glass samples were sliced and polished with thickness of 2 mm for optical measurements.

Absorption spectra were measured by a U-3900 UV-VIS spectrophotometer (Hitachi). Excitation and emission spectra were recorded on an Edinburgh Instruments FS920 spectrofluorometer by using a continuous wave 450 W Xe lamp as the excitation source, and external quantum efficiency was obtained using a BaSO4-coated integration sphere. Decay curves were performed on a Cary Eclipse spectrofluorometer (Varian Instruments). All the experiments were carried out at room temperature.

3. Results and discussion

Figure 1
Fig. 1 Transmission spectra of G-host, GSm2 and GCu2Smy (y = 0, 1, 2, 4, 6) samples.
reveals transmission spectra of G-host, GSm2 and GCu2Smy (y = 0, 1, 2, 4, 6) samples in UV-VIS regions. All samples are highly transparent (about 82%). The sharp absorption bands located at 359, 373, 402 and 470 nm in GSm2 sample can be assigned to transitions from 6H5/2 ground state to 4H7/2, 6P7/2, 4F7/2 and 4I11/2 excited states of Sm3+ ions, respectively [23

23. Z. Xia and D. Chen, “Synthesis and luminescence properties of BaMoO4:Sm3+ phosphors,” J. Am. Ceram. Soc. 93, 1397–1401 (2010).

]. Also, the absorption at 402 and 470 nm in GCu2Smy samples becomes more distinct with the increase of Sm3+ content. Significantly, compared to G-host and GSm2 samples, GCu2 and GCu2Smy samples present an obvious absorption from 250 to 380 nm, which can be generally attributed to Cu+ corresponding to the transition from ground d state to excited s states [14

14. H. Guo, R. F. Wei, and X. Y. Liu, “Tunable white luminescence and energy transfer in (Cu+)2, Eu3+ codoped sodium silicate glasses,” Opt. Lett. 37(10), 1670–1672 (2012). [CrossRef] [PubMed]

]. Besides, there is no obvious absorption band from 510 to 800 nm, which confirms that there is no Cu nanoparticles [24

24. J. Sheng, S. Chen, J. Zhang, J. Li, and J. Yu, “UV-light irradiation induced copper nanoclusters in a silicate glass,” Int. J. Hydrogen Energy 34(2), 1119–1122 (2009). [CrossRef]

] or Cu2+ [25

25. Q. Zhang, G. Chen, G. Dong, G. Zhang, X. Liu, J. Qiu, Q. Zhou, Q. Chen, and D. Chen, “The reduction of Cu2+ to Cu+ and optical properties of Cu+ ions in Cu-doped and Cu/Al-codoped high silica glasses sintered in an air atmosphere,” Chem. Phys. Lett. 482(4-6), 228–233 (2009). [CrossRef]

] in glasses.

Excitation and emission spectra of GCu2 sample are given in Fig. 2(a)
Fig. 2 (a) Excitation spectra, (b) emission spectra and (c) decay curves of GCu2 sample.
and 2(b), respectively. In excitation spectra (λem = 540 nm), a broad excitation band ranging from 250 to 360 nm with a maximum at about 330 nm is observed, arising from d→s transition of Cu+, which is consistent with the absorption band of Cu+ in Fig. 1. The high excitation intensity at 300-360 nm suggests that Cu-doped borosilicate glasses may be good candidates for UV-pumped W-LEDs. Meanwhile, under the excitation of 330 nm, GCu2 sample presents a green-yellow emitting band centered at 540 nm, corresponding to transition from s→d transition of Cu+ [14

14. H. Guo, R. F. Wei, and X. Y. Liu, “Tunable white luminescence and energy transfer in (Cu+)2, Eu3+ codoped sodium silicate glasses,” Opt. Lett. 37(10), 1670–1672 (2012). [CrossRef] [PubMed]

].

More interesting, monitored at 440 nm emission, the excitation peaks experience a blue shift from 330 to 280 nm. And the continuous shortening of the excitation wavelength results in a successive blue shift of the respective emission spectra.

Figure 3
Fig. 3 (a) Excitation spectra and (b) emission spectra of GCuy (y = 0.5, 1, 2, 3) samples.
shows (a) excitation (λem = 540 nm) and (b) emission (λex = 330 nm) spectra of GCux samples (x = 0.5, 1, 2, 3). With decreasing Cu+ content, excitation peaks in Fig. 3(a) experience a blue shift from 330 to 310 nm. And emission peaks in Fig. 3(b) show a blue shift from 560 to 460 nm also.

To further testify this point, decay curves of GCu2 sample were measured and are shown in Fig. 2(c). Non-exponential luminescence decay curves are obtained. Hence, the lifetimes are characterized by average lifetime (τ¯), and can be derived by [28

28. X. F. Liu, Y. Teng, Y. X. Zhuang, J. H. Xie, Y. B. Qiao, G. P. Dong, D. P. Chen, and J. R. Qiu, “Broadband conversion of visible light to near-infrared emission by Ce3+, Yb3+-codoped yttrium aluminum garnet,” Opt. Lett. 34(22), 3565–3567 (2009). [CrossRef] [PubMed]

],
τ¯=0tI(t)dt/0I(t)dt
(1)
where I(t) stands for the intensity at time t. The average lifetime of 540 nm emission (λex = 330 nm) is about 91 µs. However, with excitation at 280 nm and monitored at 440 nm, the decay becomes faster and the estimated average lifetime is 47 µs. The lifetimes of microsecond order are one of the specific characteristics of electric-dipole forbidden transitions of Cu+. Lifetime measurement proves these two excitation and emission bands may be attributed to Cu+ with different strength of crystal field.

As mentioned above, the luminescent color can be tuned by different excitation wavelength. Figure 4(a)
Fig. 4 (a) The CIE chromaticity diagram corresponding to emission of GCu2 and GCu2Sm2 samples for excitation wavelengths from 280 to 330 nm with 10 nm steps, photos of (b) GCu2 and (c) GCu2Sm2 samples excited by 280, 310 and 330 nm light, respectively.
and Table 1

Table 1. Chromaticity coordinates (x, y) of GCu2 and GCu2Sm2 samples under UV excitation (λex = 280, 290, 300, 310, 320 and 330 nm) and GCu2Smy (y = 1, 4, 6) samples under 330 excitation.

table-icon
View This Table
shows CIE chromaticity coordinate (x, y) of emissions of GCu2 sample for excitation wavelength from 280 to 330 nm. A 10 nm variation in excitation wavelength leads to a significant change in CIE color coordinate, and the emission shifts from blue through green white to green-yellow region. Figure 4(b) gives blue, green white and green-yellow luminescent photos of GCu2 sample taken under 280, 310 and 330 nm excitations in dark, respectively. In order to obtain perfect white-light emission, Cu+, Sm3+ co-doped samples were elaborated and investigated.

Figure 5(a)
Fig. 5 (a) Spectral overlap between excitation of GSm2 and emission of GCu2 samples. (b) Emission spectra (λex = 330) of G-host, GSm2, and GCu2Smy samples (y = 0, 1, 2, 4, 6). (c) Excitation spectra of GSm2, GCu2 and GCu2Sm2 samples. (d) Energy-level diagram of Cu+ and Sm3+ ions and possible ET process.
presents excitation spectra (λem = 600 nm) of GSm2 and emission spectra (λex = 280 nm and λex = 330 nm) of GCu2 samples. It can be clearly seen that the excitation spectra of GSm2 sample consist of several sharp peaks at 359, 373, 402 and 470 nm, which are the characteristic f-f transitions of Sm3+. The excitation bands are in agreement with the absorption bands of Sm3+ ions in Fig. 1. The peaks at 402 and 470 nm are assigned to 6H5/24F7/2 and 6H5/24I11/2 transitions, respectively.

Significantly, GSm2 sample shows an absorption band ranging from 360 to 500 nm, while GCu2 sample exhibits broad emission at 360-720 nm. It means that there is a strong overlap between emissions of Cu+ with excitation of Sm3+ in the range of 360-500 nm. Therefore, it is expected that ET process can occur from Cu+ to Sm3+.

Figure 5(b) depicts emission spectra of G-host, GSm2 and GCu2Smy samples (y = 0, 1, 2, 4, 6). Excited by 330 nm light, the optimal excitation wavelength for Cu+ but not for Sm3+, almost no emission is detected for host glass G-host and Sm3+ single-doped GSm2 samples, while emission spectra of GCu2Smy samples not only include green-yellow emission from Cu+ but also contain strong orange emission from Sm3+ with the characteristic peaks at 563 (4G5/26H5/2), 600 nm (4G5/26H7/2) and 645 nm (4G5/26H9/2) [23

23. Z. Xia and D. Chen, “Synthesis and luminescence properties of BaMoO4:Sm3+ phosphors,” J. Am. Ceram. Soc. 93, 1397–1401 (2010).

]. With increasing Sm3+ content, emission intensity of Cu+ decreases, while emission intensity of Sm3+ increases at first, reaches a maximum at y = 2, and then remarkably decreases when Sm3+ content is further increased due to concentration quenching. Especially, compared with GSm2, enhancement of Sm3+ emission by 22 times is observed in GCu2Sm2 sample. Furthermore, the external quantum efficiencies measured are about 18.6, 16.9, 17.9, 13.6 and 10.1% for GCu2Smy samples with y = 0, 1, 2, 4 and 6, respectively. And quantum efficiency may be improved by using raw materials with spectral purity, optimizing glasses composition and heat-treatment process, et, al.

Figure 5(c) gives excitation spectra of GCu2, GSm2 and GCu2Sm2 samples. Excitation spectra of Cu+, Sm3+ co-doped GCu2Sm2 sample monitored Sm3+ emission (λem = 600 nm) ranging from 250 to 360 nm is almost similiar with excitation spectra of GCu2 sample monitored at 540 nm emission of Cu+. All above phenomena indicate that high light output of Sm3+ emission actually comes from ET process from Cu+ to Sm3+. ET efficiency (η) can be estimated by the following formula [10

10. D. Geng, G. Li, M. Shang, D. Yang, Y. Zhang, Z. Cheng, and J. Lin, “Color tuning via energy transfer in Sr3In(PO4)3:Ce3+/Tb3+/Mn2+ phosphors,” J. Mater. Chem. 22(28), 14262–14271 (2012). [CrossRef]

],
η=1IS/IS0
(2)
where IS and IS0 stands for the integrated emission intensities of sensitizer Cu+ with and without activator Sm3+ present, respectively. The ET efficiencies calculated are 9.5, 14.8, 33.3 and 51.5% for GCu2Smy samples with y = 1, 2, 4 and 6, respectively.

To further validate the ET process from Cu+ to Sm3+, decay curves of emission of Cu+ were measured (Figure not shown herein). All curves are non-exponential and the average lifetimes calculated from Eq. (1) are 91, 86, 80, 75 and 71 μs for GCu2Smy samples with y = 0, 1, 2, 4 and 6, respectively. The increase of Sm3+ doping leads to faster decay, which can be attributed to ET process from Cu+ to neighboring Sm3+. The luminescent spectra, ET efficiency, and decay times of Cu+ demonstrate the presence of ET process from Cu+ to Sm3+ and that the ET process is very efficient.

Though the ET efficiencies of GCu2Sm4 and GCu2Sm6 samples are higher than 33.3%, their emission intensity in Fig. 5(b) and external quantum efficiency are low, indicating serious concentration quenching occurs for glasses doped with high Sm3+ content. To verify this phenomenon, decay curves of Sm3+ emission were measured with excitation at 470 nm and monitored at 600 nm (Figure not shown here). The average lifetimes calculated are about 2.2, 2.1, 1.7 and 1.5 ms for GCu2Smy samples with y = 1, 2, 4 and 6, respectively, implying the optimum content of Sm3+ is y = 1 or 2. This result is in accordance with that of external quantum efficiency.

The energy level diagram of Cu+ [14

14. H. Guo, R. F. Wei, and X. Y. Liu, “Tunable white luminescence and energy transfer in (Cu+)2, Eu3+ codoped sodium silicate glasses,” Opt. Lett. 37(10), 1670–1672 (2012). [CrossRef] [PubMed]

] and Sm3+ ions [23

23. Z. Xia and D. Chen, “Synthesis and luminescence properties of BaMoO4:Sm3+ phosphors,” J. Am. Ceram. Soc. 93, 1397–1401 (2010).

] and possible ET process are schematically presented in Fig. 5(d). Here Cu+ (S-S) stands for Cu+ with short distance and in strong ligand field, while Cu+ (L-W) stands for Cu+ with long distance and in weak ligand field. Cu+ (S-S) and Cu+ (L-W) model may explain the blue shift of emission spectra with the shortening of the excitation wavelength and the blue shift of excitation and emission bands with decreasing Cu+ content logically. For Cu+, Sm3+ co-doped samples, because the excited state of Cu+ and 4I11/2 and other levels of Sm3+ ions are energetically close to each other, ET process from Cu+ to Sm3+ ions can be easily proceed. An excited Cu+ relaxes from excited state to ground state nonradiatively and transfers the excitation energy to a neighboring Sm3+, promoting it from 6H5/2 ground state to 4I11/2 and other levels [Fig. 5(d), ET]. Sm3+ ions in the populated levels undergo multi-phonon relaxation to luminescent 4G5/2 level and then radiatively relax to 6HJ/2 (J = 5, 7, 9) levels, resulting in characteristic emissions of Sm3+.

It is worthwhile to notice emission of Cu+ located at green-yellow region and that of Sm3+ ions at orange region under 330 nm excitation. Combining them, tunable white-light emission can be achieved. Hence, the chromaticity coordinates of emissions of GCu2Smy (y = 0, 1, 2, 4, 6) samples excited by 330 nm light are shown in Table 1. More interesting, according to continuous emission bands of Cu+ with different distances, and efficient ET from Cu+ to Sm3+, a perfect and continuous different white-light emission bands via altering excitation wavelength can be obtained in GCu2Smy samples. Emission spectra of GCu2Sm2 sample excited by 280 to 330 nm light with 10 nm steps are given in Fig. 6
Fig. 6 Emission spectra of GCu2Sm2 sample for excitation wavelengths from 280 to 330 nm with 10 nm steps.
Their luminescent colors are characterized by CIE chromaticity diagram and are displayed in Fig. 4(a) and Table 1. It is apparent that the chromaticity coordinates of emissions of GCu2Sm2 sample gradually move from blue white to pure white (x = 0.30, y = 0.33) and into yellowish white region with increasing excitation wavelength. Figure 4(c) gives blue white, pure white and yellowish white luminescent photos of GCu2Sm2 sample taken under 280, 310 and 330 nm excitations in dark, respectively, further indicating that Cu+, Sm3+ co-doped borosilicate glasses may be used as converting phosphors for UV LED chips to generate W-LEDs.

4. Conclusions

Cu+, Sm3+ co-doped borosilicate glasses and ET from Cu+ to Sm3+ were first investigated systematically. The broad luminescence from Cu+ ranging from 380 to 720 nm was observed and the peaks shift to blue with shortening of excitation wavelength was caused by the different distribution of Cu+ with different strength of crystal field. Combined broad emission of Cu+ and sharp orange emission of Sm3+, varied hues from blue white to pure white (x = 0.30, y = 0.33) and eventually to yellow white can be generated due to efficient ET from Cu+ to Sm3+ by changing the excitation wavelength in Cu+, Sm3+ co-doped glasses. Our results may extend the understanding of interactions between Cu+ and REI, and Cu+, Sm3+ co-doped glasses may provide a new platform to design and fabricate novel luminescent materials for W-LEDs in the future.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 10904131) and the Natural Science Foundation of Zhejiang Province (No. LY12E02001). The authors also thank Prof. ShiQing Xu for the measurement of quantum efficiency.

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D. Chen, Y. Yu, H. Lin, P. Huang, F. Weng, Z. Shan, and Y. Wang, “CeF3-based glass ceramic: A potential luminescent host for white-light-emitting diode,” Opt. Lett. 34(19), 2882–2884 (2009). [CrossRef] [PubMed]

13.

H. Guo, X. Wang, J. Chen, and F. Li, “Ultraviolet light induced white light emission in Ag and Eu3+ co-doped oxyfluoride glasses,” Opt. Express 18(18), 18900–18905 (2010). [CrossRef] [PubMed]

14.

H. Guo, R. F. Wei, and X. Y. Liu, “Tunable white luminescence and energy transfer in (Cu+)2, Eu3+ codoped sodium silicate glasses,” Opt. Lett. 37(10), 1670–1672 (2012). [CrossRef] [PubMed]

15.

H. Yang, G. Lakshminarayana, Y. Teng, S. Zhou, and J. Qiu, “Tunable luminescence from Sm3+, Ce3+ codoped Al2O3-La2O3-SiO2 glasses for white light emission,” J. Mater. Res. 24(05), 1730–1734 (2009). [CrossRef]

16.

X. Liang, Y. Yang, C. Zhu, S. Yuan, G. Chen, A. Pring, and F. Xia, “Luminescence properties of Tb3+ - Sm3+ codoped glasses for white light emitting diodes,” Appl. Phys. Lett. 91(9), 091104 (2007). [CrossRef]

17.

M. Eichelbaum and K. Rademann, “Plasmonic enhancement or energy transfer? on the luminescence of gold-, silver-, and lanthanide-doped silicate glasses and its potential for light-emitting devices,” Adv. Funct. Mater. 19(13), 2045–2052 (2009). [CrossRef]

18.

J. J. Li, R. F. Wei, X. Y. Liu, and H. Guo, “Enhanced luminescence via energy transfer from Ag+ to RE ions (Dy3+, Sm3+, Tb3+) in glasses,” Opt. Express 20(9), 10122–10127 (2012). [CrossRef] [PubMed]

19.

J. D. Barrie, B. Dunn, G. Hollingsworth, and J. I. Zink, “Optical spectroscopy of copper(I)-doped Na+-β″-alumina,” J. Phys. Chem. 93(10), 3958–3963 (1989). [CrossRef]

20.

P. Boutinaud, E. Duloisy, C. Pedrini, B. Moine, C. Parent, and G. Le Flem, “Fluorescence properties of Cu+ ion in phosphate glasses of the BaLiPO4P2O5 system,” J. Solid State Chem. 94(2), 236–243 (1991). [CrossRef]

21.

K. Fukumi, A. Chayahara, K. Ohora, N. Kitamura, Y. Horino, K. Fujii, M. Makihara, J. Hayakaya, and N. Ohno, “Photoluminescence of Cu+-doped silica glass prepared by MeV ion implantation,” Nucl. Instrum. Meth. B. 149(1-2), 77–80 (1999). [CrossRef]

22.

Y. Yu, Z. Liu, N. Dai, Y. Sheng, H. Luan, J. Peng, Z. Jiang, H. Li, J. Li, and L. Yang, “Ce-Tb-Mn co-doped white light emitting glasses suitable for long-wavelength UV excitation,” Opt. Express 19(20), 19473–19479 (2011). [CrossRef] [PubMed]

23.

Z. Xia and D. Chen, “Synthesis and luminescence properties of BaMoO4:Sm3+ phosphors,” J. Am. Ceram. Soc. 93, 1397–1401 (2010).

24.

J. Sheng, S. Chen, J. Zhang, J. Li, and J. Yu, “UV-light irradiation induced copper nanoclusters in a silicate glass,” Int. J. Hydrogen Energy 34(2), 1119–1122 (2009). [CrossRef]

25.

Q. Zhang, G. Chen, G. Dong, G. Zhang, X. Liu, J. Qiu, Q. Zhou, Q. Chen, and D. Chen, “The reduction of Cu2+ to Cu+ and optical properties of Cu+ ions in Cu-doped and Cu/Al-codoped high silica glasses sintered in an air atmosphere,” Chem. Phys. Lett. 482(4-6), 228–233 (2009). [CrossRef]

26.

V. K. Tikhomirov, V. D. Rodríguez, A. Kuznetsov, D. Kirilenko, G. Van Tendeloo, and V. V. Moshchalkov, “Preparation and luminescence of bulk oxyfluoride glasses doped with Ag nanoclusters,” Opt. Express 18(21), 22032–22040 (2010). [CrossRef] [PubMed]

27.

J. J. Velázquez, V. K. Tikhomirov, L. F. Chibotaru, N. T. Cuong, A. S. Kuznetsov, V. D. Rodríguez, M. T. Nguyen, and V. V. Moshchalkov, “Energy level diagram and kinetics of luminescence of Ag nanoclusters dispersed in a glass host,” Opt. Express 20(12), 13582–13591 (2012). [CrossRef] [PubMed]

28.

X. F. Liu, Y. Teng, Y. X. Zhuang, J. H. Xie, Y. B. Qiao, G. P. Dong, D. P. Chen, and J. R. Qiu, “Broadband conversion of visible light to near-infrared emission by Ce3+, Yb3+-codoped yttrium aluminum garnet,” Opt. Lett. 34(22), 3565–3567 (2009). [CrossRef] [PubMed]

OCIS Codes
(160.2540) Materials : Fluorescent and luminescent materials
(160.2750) Materials : Glass and other amorphous materials
(160.5690) Materials : Rare-earth-doped materials
(160.6990) Materials : Transition-metal-doped materials

ToC Category:
Materials

History
Original Manuscript: September 26, 2012
Revised Manuscript: December 5, 2012
Manuscript Accepted: December 5, 2012
Published: December 20, 2012

Citation
RongFei Wei, ChongGeng Ma, YunLe Wei, JiaYu Gao, and Hai Guo, "Tunable white luminescence and energy transfer in novel Cu+, Sm3+ co-doped borosilicate glasses for W-LEDs," Opt. Express 20, 29743-29750 (2012)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-20-28-29743


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References

  1. G. Blasse and B. C. Grabmaier, Luminescent Materials (Springer, Berlin, 1994), p. 95.
  2. G. J. Gao, S. Reibstein, M. Y. Peng, and L. Wondraczek, “Tunable dual-mode photoluminescence from nanocrystalline Eu-doped Li2ZnSiO4 glass ceramic phosphors,” J. Mater. Chem.21(9), 3156–3161 (2011). [CrossRef]
  3. H. Guo, H. Zhang, J. J. Li, and F. Li, “Blue-white-green tunable luminescence from Ba2Gd2Si4O13:Ce3+,Tb3+ phosphors excited by ultraviolet light,” Opt. Express18(26), 27257–27262 (2010). [CrossRef] [PubMed]
  4. E. F. Schubert and J. K. Kim, “Solid-state light sources getting smart,” Science308(5726), 1274–1278 (2005). [CrossRef] [PubMed]
  5. P. F. Smet, A. B. Parmentier, and D. Poelman, “Selecting Conversion Phosphors for White Light-Emitting Diodes,” J. Electrochem. Soc.158(6), R37–R54 (2011). [CrossRef]
  6. W. N. Wang, T. Ogi, Y. Kaihatsu, F. Iskandar, and K. Okuyama, “Novel rare-earth-free tunable-color-emitting BCNO phosphors,” J. Mater. Chem.21(14), 5183–5189 (2011). [CrossRef]
  7. N. Guo, H. P. You, Y. H. Song, M. Yang, K. Liu, Y. H. Zheng, Y. J. Huang, and H. J. Zhang, “White-light emission from a single-emitting-component Ca9Gd(PO4)7:Eu2+, Mn2+ phosphor with tunable luminescent properties for near-UV light-emitting diodes,” J. Mater. Chem.20(41), 9061–9067 (2010). [CrossRef]
  8. C. H. Huang, W. R. Liu, and T. M. Chen, “Single-phased white-light phosphors Ca9Gd(PO4)7:Eu2+, Mn2+ under near-ultraviolet excitation,” J. Phys. Chem. C114(43), 18698–18701 (2010). [CrossRef]
  9. C. H. Huang and T. M. Chen, “A novel single-composition trichromatic white-light Ca3Y(GaO)3(BO3)4:Ce3+, Mn2+, Tb3+ phosphor for UV-light emitting diodes,” J. Phys. Chem. C115(5), 2349–2355 (2011). [CrossRef]
  10. D. Geng, G. Li, M. Shang, D. Yang, Y. Zhang, Z. Cheng, and J. Lin, “Color tuning via energy transfer in Sr3In(PO4)3:Ce3+/Tb3+/Mn2+ phosphors,” J. Mater. Chem.22(28), 14262–14271 (2012). [CrossRef]
  11. G. G. Li, D. L. Geng, M. M. Shang, C. Peng, Z. Y. Cheng, and J. Lin, “Tunable luminescence of Ce3+/Mn2+ -coactivated Ca2Gd8(SiO4)6O2 through energy transfer and modulation of excitation: potential single-phase white/yellow-emitting phosphors,” J. Mater. Chem.21(35), 13334–13344 (2011). [CrossRef]
  12. D. Chen, Y. Yu, H. Lin, P. Huang, F. Weng, Z. Shan, and Y. Wang, “CeF3-based glass ceramic: A potential luminescent host for white-light-emitting diode,” Opt. Lett.34(19), 2882–2884 (2009). [CrossRef] [PubMed]
  13. H. Guo, X. Wang, J. Chen, and F. Li, “Ultraviolet light induced white light emission in Ag and Eu3+ co-doped oxyfluoride glasses,” Opt. Express18(18), 18900–18905 (2010). [CrossRef] [PubMed]
  14. H. Guo, R. F. Wei, and X. Y. Liu, “Tunable white luminescence and energy transfer in (Cu+)2, Eu3+ codoped sodium silicate glasses,” Opt. Lett.37(10), 1670–1672 (2012). [CrossRef] [PubMed]
  15. H. Yang, G. Lakshminarayana, Y. Teng, S. Zhou, and J. Qiu, “Tunable luminescence from Sm3+, Ce3+ codoped Al2O3-La2O3-SiO2 glasses for white light emission,” J. Mater. Res.24(05), 1730–1734 (2009). [CrossRef]
  16. X. Liang, Y. Yang, C. Zhu, S. Yuan, G. Chen, A. Pring, and F. Xia, “Luminescence properties of Tb3+ - Sm3+ codoped glasses for white light emitting diodes,” Appl. Phys. Lett.91(9), 091104 (2007). [CrossRef]
  17. M. Eichelbaum and K. Rademann, “Plasmonic enhancement or energy transfer? on the luminescence of gold-, silver-, and lanthanide-doped silicate glasses and its potential for light-emitting devices,” Adv. Funct. Mater.19(13), 2045–2052 (2009). [CrossRef]
  18. J. J. Li, R. F. Wei, X. Y. Liu, and H. Guo, “Enhanced luminescence via energy transfer from Ag+ to RE ions (Dy3+, Sm3+, Tb3+) in glasses,” Opt. Express20(9), 10122–10127 (2012). [CrossRef] [PubMed]
  19. J. D. Barrie, B. Dunn, G. Hollingsworth, and J. I. Zink, “Optical spectroscopy of copper(I)-doped Na+-β″-alumina,” J. Phys. Chem.93(10), 3958–3963 (1989). [CrossRef]
  20. P. Boutinaud, E. Duloisy, C. Pedrini, B. Moine, C. Parent, and G. Le Flem, “Fluorescence properties of Cu+ ion in phosphate glasses of the BaLiPO4P2O5 system,” J. Solid State Chem.94(2), 236–243 (1991). [CrossRef]
  21. K. Fukumi, A. Chayahara, K. Ohora, N. Kitamura, Y. Horino, K. Fujii, M. Makihara, J. Hayakaya, and N. Ohno, “Photoluminescence of Cu+-doped silica glass prepared by MeV ion implantation,” Nucl. Instrum. Meth. B.149(1-2), 77–80 (1999). [CrossRef]
  22. Y. Yu, Z. Liu, N. Dai, Y. Sheng, H. Luan, J. Peng, Z. Jiang, H. Li, J. Li, and L. Yang, “Ce-Tb-Mn co-doped white light emitting glasses suitable for long-wavelength UV excitation,” Opt. Express19(20), 19473–19479 (2011). [CrossRef] [PubMed]
  23. Z. Xia and D. Chen, “Synthesis and luminescence properties of BaMoO4:Sm3+ phosphors,” J. Am. Ceram. Soc.93, 1397–1401 (2010).
  24. J. Sheng, S. Chen, J. Zhang, J. Li, and J. Yu, “UV-light irradiation induced copper nanoclusters in a silicate glass,” Int. J. Hydrogen Energy34(2), 1119–1122 (2009). [CrossRef]
  25. Q. Zhang, G. Chen, G. Dong, G. Zhang, X. Liu, J. Qiu, Q. Zhou, Q. Chen, and D. Chen, “The reduction of Cu2+ to Cu+ and optical properties of Cu+ ions in Cu-doped and Cu/Al-codoped high silica glasses sintered in an air atmosphere,” Chem. Phys. Lett.482(4-6), 228–233 (2009). [CrossRef]
  26. V. K. Tikhomirov, V. D. Rodríguez, A. Kuznetsov, D. Kirilenko, G. Van Tendeloo, and V. V. Moshchalkov, “Preparation and luminescence of bulk oxyfluoride glasses doped with Ag nanoclusters,” Opt. Express18(21), 22032–22040 (2010). [CrossRef] [PubMed]
  27. J. J. Velázquez, V. K. Tikhomirov, L. F. Chibotaru, N. T. Cuong, A. S. Kuznetsov, V. D. Rodríguez, M. T. Nguyen, and V. V. Moshchalkov, “Energy level diagram and kinetics of luminescence of Ag nanoclusters dispersed in a glass host,” Opt. Express20(12), 13582–13591 (2012). [CrossRef] [PubMed]
  28. X. F. Liu, Y. Teng, Y. X. Zhuang, J. H. Xie, Y. B. Qiao, G. P. Dong, D. P. Chen, and J. R. Qiu, “Broadband conversion of visible light to near-infrared emission by Ce3+, Yb3+-codoped yttrium aluminum garnet,” Opt. Lett.34(22), 3565–3567 (2009). [CrossRef] [PubMed]

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