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Optics Express

Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 20, Iss. 12 — Jun. 4, 2012
  • pp: 12658–12665
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Broad combined orange-red emissions from Eu2+- and Eu3+-doped low-silica calcium aluminosilicate glass

Sandro Marcio Lima, Luis Humberto da Cunha Andrade, Junior Reis Silva, Antonio Carlos Bento, Mauro Luciano Baesso, Juraci Aparecido Sampaio, Luiz Antonio de Oliveira Nunes, Yannick Guyot, and Georges Boulon  »View Author Affiliations


Optics Express, Vol. 20, Issue 12, pp. 12658-12665 (2012)
http://dx.doi.org/10.1364/OE.20.012658


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Abstract

In this paper, a broad combined orange-red emission from Eu2+- and Eu3+-doped low-silica calcium aluminosilicate (LSCAS) glass is reported. Spectroscopic results demonstrate that it is possible to tune the emission wavelength by changing the excitation wavelength in the UV-Vis region. The color coordinates for the emission spectra were calculated, and using the Commission Internationale de l’Éclairage 1931 and 1976 chromatic diagrams, it is possible to note that they are dependent on the excitation wavelength. In addition, the (u’, v’) color coordinates for the investigated LSCAS samples are close to the Planckian spectrum in the cold region between 2000 and 2600K. Our results show that the Eu:LSCAS system can be used in a white light phosphor when mixed in aggregate with phosphors using green-yellow luminescent ions.

© 2012 OSA

1. Introduction

Some rare earth ions are known to be incorporated into matrix hosts as divalent ions that exhibit a transition metal-like behavior. Among these, Eu2+ ions have attracted significant attention as a potential material for phosphors, principally due to their strong emission maximum dependence (near the blue, green and red regions of the visible region) on the material structure [5

5. Q. Zhang, X. Liu, Y. Qiao, B. Qian, G. Dong, J. Ruan, Q. Zhou, J. Qiu, and D. Chen, “Reduction of Eu3+ to Eu2+ in Eu-doped high silica glass prepared in air atmosphere,” Opt. Mater. 32(3), 427–431 (2010). [CrossRef]

9

9. S. H. M. Poort, H. M. Reijnhoudt, H. O. T. van der Kuip, and G. Blasse, “Luminescence of Eu2+ in silicate host lattices with alkaline earth ions in a row,” J. Alloy. Comp. 241(1-2), 75–81 (1996). [CrossRef]

]. In addition, Eu2+-doped materials exhibit a broad absorption band from the UV up to the blue region due to their 4f-5d transition to be sensible to the crystal field and their covalency, which makes it possible for them to be excited by different light emitting diodes.

Here, we report a broad combined orange-red emission band of Eu2+- and Eu3+-doped LSCAS glass. Spectroscopic characterization (absorption, excitation, luminescence and lifetime) indicated that the Eu2+ orange emission can be combined with the Eu3+ red emission for white light phosphors.

2. Experimental details

The glass samples, in wt%, were prepared using high-purity oxides of 41.5-x Al2O3 (5N), 47.4 CaO (5N), 7 SiO2 (5N), 2.1 MgO (5N) x Eu2O3 (4N), where x = 0.2, 0.5, 1.0, 2.0, 4.0 and 6.0. The mixture was melted under vacuum atmosphere at 1600 °C for two hours. The details regarding the glass preparation can be found elsewhere [10

10. D. F. de Sousa, L. A. O. Nunes, J. H. Rohling, and M. L. Baesso, “Laser emission at 1077 nm in Nd3+-doped calcium aluminosilicate glass,” Appl. Phys. B 77(1), 59–63 (2003). [CrossRef]

].

Optical absorption spectroscopy in the UV-Vis region was performed using a Perkin Elmer Lambda 900 spectrophotometer. The optical excitation experiments were performed using a 450 W Xe+ lamp and a H10D Jobin Yvon monochromator. The optical emission was collected by an optical fiber and analyzed by a Triax 320 Jobin Yvon monochromator with a 600 grooves/mm grating that was coupled to a Peltier cooled charge-coupled-device (CCD) detector. The excitation/emission contour plots were obtained by scanning the excitation wavelengths from 200 to 520 nm in 5-nm steps. Additional excitation spectra were recorded using a Hamamatzu Photomultiplier at different wavelengths corresponding to the maximum of the Eu2+ or Eu3+ emissions. The obtained excitation spectra were normalized using the lamp emission spectra.

Time-resolved luminescence experiments were performed to obtain the temporal behavior of the emission decay. The samples were excited with the third or fourth harmonics of a pulsed Nd3+:YAG laser (Spectra Physics, model Quanta-Ray GCR130), which delivers 10-ns pulses at a 10-Hz repetition rate. The emission of the samples was analyzed by an Oriel f-125 monochromator with a grating of 400 grooves/nm calibrated using a Hg fluorescent lamp and detected by an Instaspec V ICCD.

The luminescence quantum efficiency (η) of the samples was measured using dual-beam mode-mismatched Thermal Lens Spectroscopy (TLS). In this experimental setup, an Ar+ laser at 457 nm was used to excite the sample, and a HeNe laser at 632.8 nm was used to probe the thermal lens (TL) effect. For details on the TLS methodology, see [14

14. S. M. Lima, J. R. Silva, L. H. C. Andrade, A. Novatski, A. N. Medina, A. C. Bento, M. L. Baesso, Y. Guyot, and G. Boulon, “High values of gain cross section and luminescence quantum efficiency in OH--free Ti3+-doped low-silica calcium aluminosilicate glass,” Opt. Lett. 35(7), 1055–1057 (2010). [CrossRef] [PubMed]

].

3. Results and discussion

Figure 1
Fig. 1 Absorbance spectra for 0.5 wt% Eu2O3-doped (black line) and undoped (red line) LSCAS glasses.
shows the absorption spectra for 0.5 wt% Eu2O3-doped LSCAS and undoped LSCAS glasses. The eg absorption band of Eu2+, centered at approximately 340 nm (29400 cm−1), is clearly observed, and a superposition between the charge transfer absorption of the host glass and the t2g absorption band of Eu2+ at higher energy (> 33330 cm−1) is also observed. However, no evidence of the f-f transitions due Eu3+ is exhibited.

Contour plots of the excitation versus emission spectra obtained from LSCAS glasses doped with different Eu2O3 concentrations (0.2, 0.5, 1.0, 2.0, 4.0 and 6.0 wt.%) are shown in Fig. 2
Fig. 2 Contour plot of excitation and emission of the 0.2, 0.5, 1.0, 2.0, 4.0 and 6.0 wt% Eu2O3 LSCAS glasses. The diagonal lines are the second harmonic of the excitation source.
. The excitation was performed from 220 to 520 nm, and the emission was observed in the range between 475 and 765 nm. It is possible to observe in the combined spectra an intense luminescence between 575 and 640 nm and at approximately 700 nm, corresponding to 5D07FJ (J = 0, 1, 2, 3) and 5D07F4 emission transitions of the Eu3+ ions, respectively. These lines are observed primarily over a wide excitation band from 220 to 300 nm, and the sharp lines at 395 and at 465 nm, corresponding to the f-f transitions 7F05D3,2, are not observed in the absorption spectrum. The UV excitation region is characteristic of the Eu3+-O charge transfer energy (CTE), as noted by the absorption spectrum in Fig. 1. This UV absorption results in a red emission characteristic of the Eu3+, indicating a possible energy transfer between the host-Eu2+ and the Eu3+.

Simultaneous to the intense red emissions mentioned above, a broad emission band can also be observed from 450 to 750 nm under a broad excitation range from 250 to 475 nm, which can be assigned to the (4f65d) → 4f7 transition of the Eu2+ ions. This feature is more pronounced in the 0.5 wt.% Eu2O3-doped LSCAS glass and disappears for concentrations higher than 4 wt% Eu2O3. The excitation spectrum at 550 nm (18180 cm−1) and the emission spectrum at 350 nm (28570 cm−1) for the 0.5 wt.% Eu2O3 doped sample are shown in Fig. 3(a)
Fig. 3 Optical excitation and emission spectra of 0.5 wt% Eu2O3-doped LSCAS glass: (a) by scanning the excitation with emission monitored at 550 nm and by excitation at 350 nm and (b) by scanning the excitation with emission monitored at 618 nm and by excitation at 395 nm. (c) Schematic of the partial energy levels of europium.
. Under excitation at this wavelength, only the broad Eu2+ orange emission band is observed, which is centered at 584 nm (17125 cm−1) with a full width half maximum (FWHM) of 5450 cm−1. This band is broader than that observed in Eu:Al2O3-La2O3-SiO2 (ALSO) glass (4865 cm−1), whose emission peak position is at approximately 455 nm (21980 cm−1) [18

18. H. Yang, G. Lakshminarayana, S. Zhou, Y. Teng, and J. Qiu, “Cyan-white-red luminescence from europium doped Al2O3-La2O3-SiO2 glasses,” Opt. Express 16(9), 6731–6735 (2008). [CrossRef] [PubMed]

]. This significant red shift indicates that the Eu2+ ions are subject to a high crystal field [8

8. S. H. M. Poort, A. Meyerink, and G. Blasse, “Lifetime measurements in Eu2+-doped host lattices,” J. Phys. Chem. Solids 58(9), 1451–1456 (1997). [CrossRef]

, 9

9. S. H. M. Poort, H. M. Reijnhoudt, H. O. T. van der Kuip, and G. Blasse, “Luminescence of Eu2+ in silicate host lattices with alkaline earth ions in a row,” J. Alloy. Comp. 241(1-2), 75–81 (1996). [CrossRef]

], similar to that observed for the Ce3+:LSCAS. In this case, an emission band centered in the yellow region was observed, similar to the typical spectrum of a garnet structure [12

12. L. J. Borrero-González, I. A. A. Terra, L. A. O. Nunes, A. M. Farias, M. J. Barboza, J. H. Rohling, A. N. Medina, and M. L. Baesso, “The influence of SiO2 content on spectroscopic properties and laser emission efficiency of Yb3+-Er3+ co-doped calcium aluminolisicate glasses,” Appl. Phys. B (to be published).

, 13

13. L. H. C. Andrade, S. M. Lima, A. Novatski, P. T. Udo, N. G. C. Astrath, A. N. Medina, A. C. Bento, M. L. Baesso, Y. Guyot, and G. Boulon, “Long fluorescence lifetime of Ti3+-doped low silica calcium aluminosilicate glass,” Phys. Rev. Lett. 100(2), 027402 (2008). [CrossRef] [PubMed]

].

Figure 3(b) shows the excitation spectrum that was monitored at 618 nm (16180 cm−1) and the emission spectrum measured using excitation at a wavelength of 395 nm (25320 cm−1). These excitation and emission peaks can be better understood by examining the partial schematic energy levels diagram depicted in Fig. 3(c). The t2g and eg Eu2+ excitation bands are shifted towards longer wavelengths in the visible spectral region, with a higher shift than that observed in other europium-doped oxide systems [5

5. Q. Zhang, X. Liu, Y. Qiao, B. Qian, G. Dong, J. Ruan, Q. Zhou, J. Qiu, and D. Chen, “Reduction of Eu3+ to Eu2+ in Eu-doped high silica glass prepared in air atmosphere,” Opt. Mater. 32(3), 427–431 (2010). [CrossRef]

, 6

6. M. Nogami, T. Yamazaki, and Y. Abe, “Fluorescence properties of Eu3+ and Eu2+ in Al2O3–SiO2 glass,” J. Lumin. 78(1), 63–68 (1998). [CrossRef]

]; they also overlap with the well-known f-f transitions of Eu3+. While examining the emission spectrum, note that both Eu2+ and Eu3+ are responsible for the orange-red emissions in this glass when the excitation wavelength is at 395 nm: the broad band emission of Eu2+-doped LSCAS glass is assigned to the allowed 4f65d → 4f7 transitions, and the fluorescence emission peaks of Eu3+ are due 5D07FJ (J = 0, 1, 2, 3 and 4), which are numbered in part (c). Time-resolved luminescence measurements were performed in 0.5 wt.% Eu2O3-doped LSCAS glass by excitation at 323 nm to examine both the fast (Eu2+) and slow (Eu3+) components, as shown in Fig. 4
Fig. 4 Time-resolved luminescence of 0.5 wt% Eu2O3-doped LSCAS glass after excitation at 323 nm: (a) rapid spectral response (up to 7 μs); (b) the emission intensity decay at 550 nm; (c) slow response (up to 4 ms); (d) the emission intensity decay at 615nm.
. The eg band position (lower energy) suggests that Eu2+ ions possess cubic symmetry [6

6. M. Nogami, T. Yamazaki, and Y. Abe, “Fluorescence properties of Eu3+ and Eu2+ in Al2O3–SiO2 glass,” J. Lumin. 78(1), 63–68 (1998). [CrossRef]

]. Furthermore, a very large Stokes shift of approximately 1000 cm−1 is observed in this glass. This shift can be interpreted by the glass optical basicity, as suggested by Wang et al., who investigated Eu-doped borate glasses [19

19. C. Wang, M. Peng, N. Jiang, X. Jiang, C. Zhao, and J. Qiu, “Tuning the Eu luminescence in glass materials synthesized in air by adjusting glass compositions,” Mater. Lett. 61(17), 3608–3611 (2007). [CrossRef]

] and suggested that in a system with high optical basicity, there is a red shift in the Eu2+ absorption bands. The optical basicity for the LSCAS system was recently determined to be 0.83 [20

20. A. Novatski, A. Steimacher, A. N. Medina, A. C. Bento, M. L. Baesso, L. H. C. Andrade, S. M. Lima, Y. Guyot, and G. Boulon, “Relations among nonbridging oxygen, optical properties, optical basicity, and color center formation in CaO-MgO aluminosilicate glasses,” J. Appl. Phys. 104(9), 094910 (2008). [CrossRef]

]; this value is greater than those obtained from soda-lime (~0.6) [21

21. J. A. Duffy, “Chemical bonding in the oxides of the elements: a new appraisal,” J. Solid State Chem. 62(2), 145–157 (1986). [CrossRef]

], phosphate (~0.5) [22

22. D. Ehrt, P. Ebeling, and U. Natura, “UV Transmission and radiation-induced defects in phosphate and fluoride-phosphate glasses,” J. Non-Cryst. Solids 263-264, 240–250 (2000). [CrossRef]

] and borate (0.48-0.59) [15

15. J. A. Sampaio, M. C. Filadelpho, A. A. Andrade, J. H. Rohling, A. N. Medina, A. C. Bento, L. M. da Silva, F. C. G. Gandra, L. A. O. Nunes, and M. L. Baesso, “Study on the observation of Eu2+ and Eu3+ valence states in low silica calcium aluminosilicate glasses,” J. Phys. Condens. Matter 22(5), 055601 (2010). [CrossRef] [PubMed]

] glasses, which reinforces the assumption of Wang et al.

The decay curve of the fast Eu2+ fluorescence observed in Fig. 4(b) is non-exponential, primarily due to the distribution of Eu2+ sites in the host, as previously observed for Yb3+- and Ce3+-doped LSCAS glasses [11

11. Y. Guyot, A. Steimacher, M. P. Belançon, A. N. Medina, M. L. Baesso, S. M. Lima, L. H. C. Andrade, A. Brenier, A. M. Jurdyc, and G. Boulon, “Spectroscopic properties, concentration quenching, and laser investigations of Yb3+-doped calcium aluminosilicate glasses,” J. Opt. Soc. Am. B 28(10), 2510–2517 (2011). [CrossRef]

, 15

15. J. A. Sampaio, M. C. Filadelpho, A. A. Andrade, J. H. Rohling, A. N. Medina, A. C. Bento, L. M. da Silva, F. C. G. Gandra, L. A. O. Nunes, and M. L. Baesso, “Study on the observation of Eu2+ and Eu3+ valence states in low silica calcium aluminosilicate glasses,” J. Phys. Condens. Matter 22(5), 055601 (2010). [CrossRef] [PubMed]

, 16

16. L. H. C. Andrade, S. M. Lima, A. Novatski, A. Steimacher, J. H. Rohling, A. N. Medina, A. C. Bento, M. L. Baesso, Y. Guyot, and G. Boulon, “A step forward toward smart white lighting: combination of glass phosphor and light emitting diodes,” Appl. Phys. Lett. 95(8), 081104 (2009). [CrossRef]

]. By integrating the curve in (b), an average lifetime of 1.0 μs was determined. This lifetime value is reasonable for the allowed transition, 4f65d1 → 4f7 (or 5d → 4f for Eu2+), and it is in agreement with the characteristics of other Eu2+-doped systems found in the literature [23

23. X. Zhang, J. Wang, J. Zhang, and Q. Su, “Photoluminescence properties of Eu2+ doped Ba2ZnS3 phosphor for white light emitting diodes,” Mater. Lett. 61(3), 761–764 (2007). [CrossRef]

]. Considering the long Eu3+ luminescence at 620 nm, the dynamic is well-fitted by a single exponential function, yielding a lifetime of approximately 1.1 ms.

The lifetime values for both Eu2+ and Eu3+ for the 0.5 wt.% Eu2O3-doped LSCAS glass (5 × 1019 ions/cm3) are near the value found in the literature for fluoro-phosphate glass with (mol%) 10Sr(PO3)2, 10 MgF2, 30 CaF2, 15SrF2 and 35 AlF3 doped with 5 × 1019 ions/cm3 of Eu2O3 [20

20. A. Novatski, A. Steimacher, A. N. Medina, A. C. Bento, M. L. Baesso, L. H. C. Andrade, S. M. Lima, Y. Guyot, and G. Boulon, “Relations among nonbridging oxygen, optical properties, optical basicity, and color center formation in CaO-MgO aluminosilicate glasses,” J. Appl. Phys. 104(9), 094910 (2008). [CrossRef]

]. Although Eu3+ and Eu2+ emit in the same orange-red regions, no evidence of any energy transfer mechanism was observed by the time-resolved luminescence study.

To assess the Eu2O3-doped LSCAS glass emission in the orange-red region and their dependence on the excitation wavelength, their emission spectra for excitation at 394, 405 and 465 nm were deconvoluted using the three color matching functions established by the Commission Internationale de l’Éclairage (CIE) in 1931, known as the CIE 1931 x-y color matching functions [24

24. J. Guild, “The colorimetric properties of the spectrum,” Philos. Trans. R. Soc. London, Ser. A 230, 149–187 (1931).

]. Figure 5
Fig. 5 CIE 1931 x-y chromatic diagram showing the position of 0.5 wt% Eu2O3-doped LSCAS glass for three different excitation wavelengths, the position of 2.0 wt% CeO2-doped LSCAS glass for an excitation wavelength of 405 nm, the white light position (0.33, 0.33), the UV LED 405 nm position and the Planckian spectrum from 2000 to 20000K.
shows these calculated coordinates for each excitation wavelength in the (x, y) chromaticity diagram. Note that the coordinates are strongly dependent on the excitation wavelength and that the coordinates are located in the orange-red region. By combining the glass emission with the 405 nm component of the UV LED used to excite phosphors, the color coordinates can be displaced along the dotted line.

An important parameter for evaluating a visible light source is the previously mentioned correlated color temperature (CCT), which is a specification of the color appearance of the light emitted relating its color to the color of light from an ideal black-body radiator reference source at a particular temperature. The black-body spectrum is considered an ideal spectrum due its similarity with the day light spectrum. The CCT is determined by evaluating the distance from the color coordinates to the Planckian locus. However, this distance can only be calculated in a perceptual uniform color diagram known as the CIE 1976 (u’, v’) color space, which is a transformation of the CIE 1931. Therefore, the distance from the Planckian locus to the (u’, v’) color coordinate (Duv) indicates how close the tested light source is to the ideal source and its CCT [13

13. L. H. C. Andrade, S. M. Lima, A. Novatski, P. T. Udo, N. G. C. Astrath, A. N. Medina, A. C. Bento, M. L. Baesso, Y. Guyot, and G. Boulon, “Long fluorescence lifetime of Ti3+-doped low silica calcium aluminosilicate glass,” Phys. Rev. Lett. 100(2), 027402 (2008). [CrossRef] [PubMed]

]. Table 1

Table 1. Color Coordinates, Duv and Correlated Color Temperature (CCT) for the 394-, 405- and 465-nm Excitation Wavelengths

table-icon
View This Table
summarizes the color coordinates, Duv and CCT, for three different excitations. The excitations at 394 and 465 nm both match the Eu3+ absorption lines, and their red emission lines are responsible for the low CCT values. Under 405 nm excitation, the Eu:LSCAS glass exhibits broader emission due to Eu2+, which displaces the color coordinates to the orange and consequently increases the CCT. The Duv values indicate that the color coordinates are near the Planck locus. Note that the Duv calculated values in Table 1 do not consider the contribution of the excitation source; this if the Duv was considered, it could assume the lowest values that are closest to the Planckian locus.

The 0.5 wt.% Eu2O3-doped LSCAS glass exhibits the highest luminescence quantum efficiency (approximately 50%) among the samples studied. Note that our measured η value does not distinguish the contributions of the Eu3+ and Eu2+ emissions. When the sample is excited at 457 nm, the entire emission band is integrated and the average emission wavelength is considered to determine η. The resulting η value for our system is considerably higher than the η = 8% reported in the literature for Eu2+:SrBA glass [25

25. Y. Li, P. Niu, C. Tang, and L. Hu, “Blue-excited luminescence of Eu-doped strontium boroaluminate glasses,” J. Lumin. 128(2), 273–276 (2008). [CrossRef]

] and also the η = 30% reported in the literature for Eu2+:Sr2SiS4 phosphor [26

26. A. B. Parmentier, P. F. Smet, F. Bertram, J. Christen, and D. Poelman, “Structure and luminescence of (Ca,Sr)2SiS4:Eu2+ phosphors,” J. Phys. D Appl. Phys. 43(8), 085401 (2010). [CrossRef]

].

4. Conclusions

In this work, a systematic study was performed on the excitation and time-resolved emission luminescence of Eu-doped LSCAS glasses. Our results showed that the coexistence of Eu2+ and Eu3+, which is induced by preparing the sample under vacuum atmosphere, provides a broad combined orange-red emission when the sample is excited in the UV-blue region. In addition, this emission can be tuned according to the excitation wavelength used. The emission peak shifting towards longer wavelength is interpreted in terms of the larger basicity than in other glass systems. The emission peak position near the orange region indicates that this is a potential material for use in phosphors, which is supported by the good values of Duv, which indicate that the color coordinates are near the Planckian curve.

Acknowledgments

The authors thank CAPES/COFECUB Brazil/France cooperation Grant No. 565/07, Fundação Araucária, FUNDECT, CNPq, FINEP and CNRS-UCBLyon1 for their financial support.

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M. Nogami, T. Yamazaki, and Y. Abe, “Fluorescence properties of Eu3+ and Eu2+ in Al2O3–SiO2 glass,” J. Lumin. 78(1), 63–68 (1998). [CrossRef]

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T.-W. Kuo, W.-R. Liu, and T.-M. Chen, “High color rendering white light-emitting-diode illuminator using the red-emitting Eu2+-activated CaZnOS phosphors excited by blue LED,” Opt. Express 18(8), 8187–8192 (2010). [CrossRef]

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S. H. M. Poort, A. Meyerink, and G. Blasse, “Lifetime measurements in Eu2+-doped host lattices,” J. Phys. Chem. Solids 58(9), 1451–1456 (1997). [CrossRef]

9.

S. H. M. Poort, H. M. Reijnhoudt, H. O. T. van der Kuip, and G. Blasse, “Luminescence of Eu2+ in silicate host lattices with alkaline earth ions in a row,” J. Alloy. Comp. 241(1-2), 75–81 (1996). [CrossRef]

10.

D. F. de Sousa, L. A. O. Nunes, J. H. Rohling, and M. L. Baesso, “Laser emission at 1077 nm in Nd3+-doped calcium aluminosilicate glass,” Appl. Phys. B 77(1), 59–63 (2003). [CrossRef]

11.

Y. Guyot, A. Steimacher, M. P. Belançon, A. N. Medina, M. L. Baesso, S. M. Lima, L. H. C. Andrade, A. Brenier, A. M. Jurdyc, and G. Boulon, “Spectroscopic properties, concentration quenching, and laser investigations of Yb3+-doped calcium aluminosilicate glasses,” J. Opt. Soc. Am. B 28(10), 2510–2517 (2011). [CrossRef]

12.

L. J. Borrero-González, I. A. A. Terra, L. A. O. Nunes, A. M. Farias, M. J. Barboza, J. H. Rohling, A. N. Medina, and M. L. Baesso, “The influence of SiO2 content on spectroscopic properties and laser emission efficiency of Yb3+-Er3+ co-doped calcium aluminolisicate glasses,” Appl. Phys. B (to be published).

13.

L. H. C. Andrade, S. M. Lima, A. Novatski, P. T. Udo, N. G. C. Astrath, A. N. Medina, A. C. Bento, M. L. Baesso, Y. Guyot, and G. Boulon, “Long fluorescence lifetime of Ti3+-doped low silica calcium aluminosilicate glass,” Phys. Rev. Lett. 100(2), 027402 (2008). [CrossRef] [PubMed]

14.

S. M. Lima, J. R. Silva, L. H. C. Andrade, A. Novatski, A. N. Medina, A. C. Bento, M. L. Baesso, Y. Guyot, and G. Boulon, “High values of gain cross section and luminescence quantum efficiency in OH--free Ti3+-doped low-silica calcium aluminosilicate glass,” Opt. Lett. 35(7), 1055–1057 (2010). [CrossRef] [PubMed]

15.

J. A. Sampaio, M. C. Filadelpho, A. A. Andrade, J. H. Rohling, A. N. Medina, A. C. Bento, L. M. da Silva, F. C. G. Gandra, L. A. O. Nunes, and M. L. Baesso, “Study on the observation of Eu2+ and Eu3+ valence states in low silica calcium aluminosilicate glasses,” J. Phys. Condens. Matter 22(5), 055601 (2010). [CrossRef] [PubMed]

16.

L. H. C. Andrade, S. M. Lima, A. Novatski, A. Steimacher, J. H. Rohling, A. N. Medina, A. C. Bento, M. L. Baesso, Y. Guyot, and G. Boulon, “A step forward toward smart white lighting: combination of glass phosphor and light emitting diodes,” Appl. Phys. Lett. 95(8), 081104 (2009). [CrossRef]

17.

L. H. C. Andrade, S. M. Lima, M. L. Baesso, A. Novatski, J. H. Rohling, Y. Guyot, and G. Boulon, “Tunable light emission and similarities with garnet structure of Ce-doped LSCAS glass for white-light devices,” J. Alloy. Comp. 510(1), 54–59 (2012). [CrossRef]

18.

H. Yang, G. Lakshminarayana, S. Zhou, Y. Teng, and J. Qiu, “Cyan-white-red luminescence from europium doped Al2O3-La2O3-SiO2 glasses,” Opt. Express 16(9), 6731–6735 (2008). [CrossRef] [PubMed]

19.

C. Wang, M. Peng, N. Jiang, X. Jiang, C. Zhao, and J. Qiu, “Tuning the Eu luminescence in glass materials synthesized in air by adjusting glass compositions,” Mater. Lett. 61(17), 3608–3611 (2007). [CrossRef]

20.

A. Novatski, A. Steimacher, A. N. Medina, A. C. Bento, M. L. Baesso, L. H. C. Andrade, S. M. Lima, Y. Guyot, and G. Boulon, “Relations among nonbridging oxygen, optical properties, optical basicity, and color center formation in CaO-MgO aluminosilicate glasses,” J. Appl. Phys. 104(9), 094910 (2008). [CrossRef]

21.

J. A. Duffy, “Chemical bonding in the oxides of the elements: a new appraisal,” J. Solid State Chem. 62(2), 145–157 (1986). [CrossRef]

22.

D. Ehrt, P. Ebeling, and U. Natura, “UV Transmission and radiation-induced defects in phosphate and fluoride-phosphate glasses,” J. Non-Cryst. Solids 263-264, 240–250 (2000). [CrossRef]

23.

X. Zhang, J. Wang, J. Zhang, and Q. Su, “Photoluminescence properties of Eu2+ doped Ba2ZnS3 phosphor for white light emitting diodes,” Mater. Lett. 61(3), 761–764 (2007). [CrossRef]

24.

J. Guild, “The colorimetric properties of the spectrum,” Philos. Trans. R. Soc. London, Ser. A 230, 149–187 (1931).

25.

Y. Li, P. Niu, C. Tang, and L. Hu, “Blue-excited luminescence of Eu-doped strontium boroaluminate glasses,” J. Lumin. 128(2), 273–276 (2008). [CrossRef]

26.

A. B. Parmentier, P. F. Smet, F. Bertram, J. Christen, and D. Poelman, “Structure and luminescence of (Ca,Sr)2SiS4:Eu2+ phosphors,” J. Phys. D Appl. Phys. 43(8), 085401 (2010). [CrossRef]

OCIS Codes
(160.2540) Materials : Fluorescent and luminescent materials
(160.2750) Materials : Glass and other amorphous materials
(300.6550) Spectroscopy : Spectroscopy, visible
(330.7310) Vision, color, and visual optics : Vision

ToC Category:
Materials

History
Original Manuscript: February 21, 2012
Revised Manuscript: April 25, 2012
Manuscript Accepted: April 26, 2012
Published: May 21, 2012

Citation
Sandro Marcio Lima, Luis Humberto da Cunha Andrade, Junior Reis Silva, Antonio Carlos Bento, Mauro Luciano Baesso, Juraci Aparecido Sampaio, Luiz Antonio de Oliveira Nunes, Yannick Guyot, and Georges Boulon, "Broad combined orange-red emissions from Eu2+- and Eu3+-doped low-silica calcium aluminosilicate glass," Opt. Express 20, 12658-12665 (2012)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-20-12-12658


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References

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  13. L. H. C. Andrade, S. M. Lima, A. Novatski, P. T. Udo, N. G. C. Astrath, A. N. Medina, A. C. Bento, M. L. Baesso, Y. Guyot, and G. Boulon, “Long fluorescence lifetime of Ti3+-doped low silica calcium aluminosilicate glass,” Phys. Rev. Lett.100(2), 027402 (2008). [CrossRef] [PubMed]
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  23. X. Zhang, J. Wang, J. Zhang, and Q. Su, “Photoluminescence properties of Eu2+ doped Ba2ZnS3 phosphor for white light emitting diodes,” Mater. Lett.61(3), 761–764 (2007). [CrossRef]
  24. J. Guild, “The colorimetric properties of the spectrum,” Philos. Trans. R. Soc. London, Ser. A230, 149–187 (1931).
  25. Y. Li, P. Niu, C. Tang, and L. Hu, “Blue-excited luminescence of Eu-doped strontium boroaluminate glasses,” J. Lumin.128(2), 273–276 (2008). [CrossRef]
  26. A. B. Parmentier, P. F. Smet, F. Bertram, J. Christen, and D. Poelman, “Structure and luminescence of (Ca,Sr)2SiS4:Eu2+ phosphors,” J. Phys. D Appl. Phys.43(8), 085401 (2010). [CrossRef]

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