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Optics Express

Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 19, Iss. 23 — Nov. 7, 2011
  • pp: 23436–23443
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Unusual luminescence quenching and reviving behavior of Bi-doped germanate glasses

Beibei Xu, Shifeng Zhou, Miaojia Guan, Dezhi Tan, Yu Teng, Jiajia Zhou, Zhijun Ma, Zhanglian Hong, and Jianrong Qiu  »View Author Affiliations


Optics Express, Vol. 19, Issue 23, pp. 23436-23443 (2011)
http://dx.doi.org/10.1364/OE.19.023436


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Abstract

Here for the first time, we report an unusual annealing temperature dependent near-infrared (NIR) luminescence quenching and reviving behavior in Bi-doped MgO-Al2O3-GeO2 glasses. Systematic characterizations of the samples by using differential thermal analysis (DTA), photoluminescence and absorption spectra, X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicate that this phenomenon is associated with the reversible reaction of Bi+ and Bi0 initiated by the change of local glass structure. Excitingly, wavelength tunable luminescence is also observed and it can be ascribed to selective excitation of active Bi+ center in different sites. These results not only open a new way for controlling luminescence properties of main group elements in glass but also provide great value for improving practical active-fiber drawing process.

© 2011 OSA

1. Introduction

With the rapid development of telecommunication technology, optical fiber transmission with super-high-speed and super-big-capacity is demanded. At present, the optical amplification bandwidth of the widely used rare-earth ions doped fiber amplifiers is limited due to the luminescence nature based on 4f-4f electronic transitions of rare earth ions [1

1. M. Yamada, H. Ono, and Y. Ohishi, “Low-noise, broadband Er3+-doped silica fiber amplifiers,” Electron. Lett. 34(15), 1490–1491 (1998). [CrossRef]

]. For this reason, broadband fiber amplifier has attracted increasing attention since it can be used to compensate for the signal loss in the transmission fiber with a broad bandwidth. Bi-doped glasses are of considerable current interest, primarily for their ultra-broad and tunable near-infrared (NIR) emission in the region from 1000 to 1700 nm with full width at half maximum (FWHM) over 300 nm [2

2. S. Zhou, N. Jiang, B. Zhu, H. Yang, S. Ye, G. Lakshminarayana, J. Hao, and J. Qiu, “Multifunctional bismuth-doped nanoporous silica glass: from blue-green, orange, red, and white light sources to ultra-broadband infrared amplifiers,” Adv. Funct. Mater. 18(9), 1407–1413 (2008). [CrossRef]

10

10. V. V. Dvoyrin, V. M. Mashinsky, L. I. Bulatov, I. A. Bufetov, A. V. Shubin, M. A. Melkumov, E. F. Kustov, E. M. Dianov, A. A. Umnikov, V. F. Khopin, M. V. Yashkov, and A. N. Guryanov, “Bismuth-doped-glass optical fibers-a new active medium for lasers and amplifiers,” Opt. Lett. 31(20), 2966–2968 (2006). [CrossRef] [PubMed]

]. Significantly, optical fibers [10

10. V. V. Dvoyrin, V. M. Mashinsky, L. I. Bulatov, I. A. Bufetov, A. V. Shubin, M. A. Melkumov, E. F. Kustov, E. M. Dianov, A. A. Umnikov, V. F. Khopin, M. V. Yashkov, and A. N. Guryanov, “Bismuth-doped-glass optical fibers-a new active medium for lasers and amplifiers,” Opt. Lett. 31(20), 2966–2968 (2006). [CrossRef] [PubMed]

,11

11. I. A. Bufetov, K. M. Golant, S. V. Firstov, A. V. Kholodkov, A. V. Shubin, and E. M. Dianov, “Bismuth activated alumosilicate optical fibers fabricated by surface-plasma chemical vapor deposition technology,” Appl. Opt. 47(27), 4940–4944 (2008). [CrossRef] [PubMed]

], broadband fiber amplifiers [10

10. V. V. Dvoyrin, V. M. Mashinsky, L. I. Bulatov, I. A. Bufetov, A. V. Shubin, M. A. Melkumov, E. F. Kustov, E. M. Dianov, A. A. Umnikov, V. F. Khopin, M. V. Yashkov, and A. N. Guryanov, “Bismuth-doped-glass optical fibers-a new active medium for lasers and amplifiers,” Opt. Lett. 31(20), 2966–2968 (2006). [CrossRef] [PubMed]

,12

12. I. A. Bufetov, S. V. Firstov, V. F. Khopin, O. I. Medvedkov, A. N. Guryanov, and E. M. Dianov, “Bi-doped fiber lasers and amplifiers for a spectral region of 1300-1470 nm,” Opt. Lett. 33(19), 2227–2229 (2008). [CrossRef] [PubMed]

], fiber lasers [12

12. I. A. Bufetov, S. V. Firstov, V. F. Khopin, O. I. Medvedkov, A. N. Guryanov, and E. M. Dianov, “Bi-doped fiber lasers and amplifiers for a spectral region of 1300-1470 nm,” Opt. Lett. 33(19), 2227–2229 (2008). [CrossRef] [PubMed]

,13

13. I. Razdobreev, L. Bigot, V. Pureur, A. Favre, G. Bouwmans, and M. Douay, “Efficient all-fiber bismuth-doped laser,” Appl. Phys. Lett. 90(3), 031103 (2007). [CrossRef]

], ultrashort pulsed lasers [14

14. V. V. Dvoyrin, V. M. Mashinsky, and E. M. Dianov, “Yb-Bi pulsed fiber lasers,” Opt. Lett. 32(5), 451–453 (2007). [CrossRef] [PubMed]

] and optical waveguides [15

15. N. D. Psaila, R. R. Thomson, H. T. Bookey, A. K. Kar, N. Chiodo, R. Osellame, G. Cerullo, G. Brown, A. Jha, and S. Shen, “Femtosecond laser inscription of optical waveguides in Bismuth ion doped glass,” Opt. Express 14(22), 10452–10459 (2006). [CrossRef] [PubMed]

,16

16. B. Zhou, H. Lin, B. Chen, and E. Y. B. Pun, “Superbroadband near-infrared emission in Tm-Bi codoped sodium-germanium-gallate glasses,” Opt. Express 19(7), 6514–6523 (2011). [CrossRef] [PubMed]

] have been prepared and constructed from Bi doped glasses, which indicate that practical devices can be fabricated using Bi-doped materials. Among them, fiber is one of the most important physical forms for the practical application of Bi-doped materials. Although the success of fabrication of Bi-doped fiber has been reported [9

9. I. A. Bufetov and E. M. Dianov, “Bi-doped fiber lasers,” Laser Phys. Lett. 6(7), 487–504 (2009). [CrossRef]

11

11. I. A. Bufetov, K. M. Golant, S. V. Firstov, A. V. Kholodkov, A. V. Shubin, and E. M. Dianov, “Bismuth activated alumosilicate optical fibers fabricated by surface-plasma chemical vapor deposition technology,” Appl. Opt. 47(27), 4940–4944 (2008). [CrossRef] [PubMed]

,17

17. V. G. Truong, L. Bigot, A. Lerouge, M. Douay, and I. Razdobreev, “Study of thermal stability and luminescence quenching properties of bismuth-doped silicate glasses for fiber laser applications,” Appl. Phys. Lett. 92(4), 041908 (2008). [CrossRef]

], there is no systematic investigation about the luminescence property change during the optical fiber preparation process.

2. Experimental

Glass samples with the compositions of 75GeO2-20MgO-5Al2O3-xBi2O3 (x = 0, 0.5, 1.0, 2.0, in mol%) were prepared by the melt-quenching method using analytical grade reagents MgO, Al2O3, GeO2 and Bi2O3 as raw materials. A 30 g batch was mixed homogeneously in agate mortar and then melted in a corundum crucible at 1500 °C for 30 min in air. The melt was cast onto a stainless steel plate and then annealed at 350 °C for 2 h. The obtained glass sample was cut and polished into pieces with the size of 5 × 5 × 2 mm3. The glass samples were heat treated at 670-890 °C for 5 hours with a heating rate of 5 °C/min in a small programmed electric furnace. The as-made and heat-treated glass samples are simplified as xB and xBy, respectively, where x represents the concentration of Bi2O3 in mol% (0.5, 1.0, 2.0), and y is the heat-treatment temperature (y = 670, 690, 710, 730, 750, 770, 790, 810, 830, 850, 870, 890). In order to eliminate the possibility of NIR photoluminescence from Bi-doped MgGeO3 and GeO2 crystals, MgGeO3 and GeO2 crystals with Bi doping concentration of 1.0 mol% were also prepared for comparison by sintering the batches in a programmed electric furnace at 1250 °C and 950 °C, respectively.

The differential thermal analysis (DTA) was carried out by a CRY-Z Differential Thermal Analyzer at a heating rate of 10 °C/min. Photoluminescence spectra were recorded using a FLS920 fluorescence spectrophotometer (Edinburgh Instrument Ltd., U.K.). Absorption spectra were recorded using a UV-3150 UV-Vis-NIR spectrophotometer (Shimadzu Corp., Japan). X-ray diffraction (XRD) measurements were carried out using a D/MAX-2550pc diffractometer with Cu Kα as the incident radiation source. TEM was performed in a Tecnai G2 F30 S-Twin Transmission electron microscopy (Philips-FEI Corp., Netherlands).

3. Results and discussion

In order to investigate the effect of heat-treatment temperature on the optical properties of Bi-doped glasses, DTA analysis of Bi-doped glasses 0.5B and 2.0B has been performed and the results are shown in Fig. 1
Fig. 1 DTA curves of glasses 0.5B and 2.0B.
. The glass transition of two glasses occurred at 666 °C. The crystallization onset temperature Tx and maximum crystallization temperature TC of glass 0.5B are 804 °C and 840 °C, respectively. However, Tx and TC of glass 2.0B are 788 °C and 830 °C, respectively, which are lower than those of glass 0.5B. This indicates that the addition of Bi2O3 may lower the crystallization temperature and promote the nucleation and crystallization process of glass. As △T > 100 °C (△T = Tx - Tg), the glasses can be considered to have good thermal stability against crystallization [18

18. L. Le Neindre, S. Jiang, B. Hwang, T. Luo, J. Watson, and N. Peyghambarian, “Effect of relative alkali content on absorption linewidth in erbium-doped tellurite glasses,” J. Non-Cryst. Solids 255(1), 97–102 (1999). [CrossRef]

].

Figure 2(a)
Fig. 2 (a) NIR emission spectra of glass 0.5B excited by 480, 680 and 800 nm, respectively. (b) Dependence of NIR emission intensity on Bi dopant concentration (the concentration is 0.5, 1.0, and 2.0 mol%, respectively) with different excitation wavelength (480, 680, and 800 nm). (c) NIR emission spectra of glass 0.5B after heat-treatment at different temperatures excited by 800 nm. (d)‑(f) Heat-treatment temperature-dependent NIR emission relative intensity of glass 0.5B excited by 480, 680, and 800 nm respectively. (g)‑(h) Heat-treatment temperature-dependent relative intensity of glasses excited by 800 nm (g), (h) corresponding to glasses 1.0B and 2.0B, respectively). The NIR emission intensity of (d)‑(h) is relative to the intensity of glasses 0.5B, 1.0B and 2.0B before heat-treatment, respectively.
shows the NIR emission spectra of glass 0.5B, which covers the region of 1000~1600 nm. Under excitation at 480, 680 and 800 nm, the broadband NIR emission was observed centering at about 1052, 1143, and 1239 nm, respectively. Similar NIR emission has been reported in Bi-doped germinosilicate glass and germanium glass, and it has been ascribed to the 3P13P0 electronic transition of Bi+ ions in multiple sites [5

5. J. Ren, G. Dong, S. Xu, R. Bao, and J. Qiu, “Inhomogeneous broadening, luminescence origin and optical amplification in bismuth-doped glass,” J. Phys. Chem. A 112(14), 3036–3039 (2008). [CrossRef] [PubMed]

,19

19. S. Zhou, H. Dong, H. Zeng, J. Hao, J. Chen, and J. Qiu, “Infrared luminescence and amplification properties of Bi-doped GeO2−Ga2O3−Al2O3 glasses,” J. Appl. Phys. 103(10), 103532 (2008). [CrossRef]

]. Maximum emission intensity of glasses before heat-treatment appears at the Bi dopant concentration of 1.0 mol% [Fig. 2(b)]. As shown in Fig. 2(c)–(f), when glass 0.5B is heat-treated at different temperatures, NIR emission intensity shows a great change with increasing temperature and the whole process can be divided into three stages. (1) The first stage: the emission intensity decreases as the heat-treatment temperature increases from glass transition temperature (~670 °C) to around 750 °C. It is necessary to mention that the NIR emission intensity has already decreased to about half the value of the as-made glass when the glass was heat-treated at 670 °C which is very close to the glass transition temperature (666 °C). This indicates that when the optical fiber preparation process was conducted around the glass transition temperature, it should be controlled concisely in order to avoid the drastic decrease of luminescence intensity. (2) The second stage: the NIR emission has mostly disappeared when the glass was heat-treated at 730 °C. This shows that optical fiber made by Bi-doped MgO-Al2O3-GeO2 glass cannot be prepared around this temperature. Fortunately, as the temperature goes up to 750 °C, NIR luminescence gradually starts to recover and the emission intensity reaches the maximum at around 810 °C. It is obviously that the emission intensity of the glass heat-treated at 810 °C is higher than that of the sample annealed at 670 °C. Hence, this unusual luminescence reviving process opens up an exciting opportunity for choosing appropriate fiber drawing temperature. (3) The third stage: further increasing the temperature results in the decrease of the emission intensity again. The NIR emission disappears finally at around 890 °C.

Except for the heat-treatment dependent intensity change, we also find that this dependence can be affected by excitation wavelength and dopant concentration. A few differences are observed when the glasses are excited by 480, 680 and 800 nm [Fig. 2(d)‑(f)], which confirms that the excitation wavelength dependent emission peak shift is ascribed to the electronic transition 3P13P0 of Bi+ ions in distinct sites. Due to the different chemical environment of the distinct sites, these differences may occur when the glasses are excited by different wavelength. Figure 2(g) and (h) show the intensity change of glasses 1.0B and 2.0B. The relationship between NIR emission intensity and heat-treatment temperature varies greatly with the increase of Bi dopant concentration. In the first stage, NIR emission intensity vanishes at around 730 °C for glasses 0.5B and 1.0B, but 710 °C for glass 2.0B. In the second stage, the emission intensity increases faster for glass 0.5B than glass 1.0B, and faster for glass 1.0B than glass 2.0B. The emission intensity for glasses 0.5B and 1.0B reaches the maximum value at 810 °C, yet 790 °C for glass 2.0B. Furthermore, the maximum value is much higher for glass 0.5B (about 80% of the emission intensity for glass 0.5B before heat-treatment) than glass 1.0B (about 40%) and glass 2.0B (about 10%). In the third stage, the emission intensity vanishes at around 890 °C for glass 0.5B, but 870 °C for glass 1.0B and 850 °C for glass 2.0B. We will discuss the origin of the relationship between NIR emission intensity and heat-treatment temperature later.

To elucidate the origin of heat-treatment dependent NIR luminescence change, we measured the absorption spectra of the glasses. Figure 3
Fig. 3 Absorption spectra of glasses (a) 0.5B, (b) 0.5B690, (c) 0.5B750, (d) 0.5B810. The insets (e)‑(h) are pictures of glasses 0.5B, 0.5B690, 0.5B750 and 0.5B810, respectively.
shows the absorption spectra of glass 0.5B and the heat-treated glasses 0.5B690, 0.5B750 and 0.5B810. As shown in the inset of Fig. 3, the color of these glasses turns from reddish orange to yellow-brown and then to black, and finally to brown again with increasing heat-treatment temperature. It is reported that Bi ions are very sensitive to preparation conditions and can readily reduced to Bi atoms at high temperature. Darking effect of Bi-doped glasses has been ascribed to the precipitation and agglomeration of Bi metallic colloid [20

20. M. Peng, C. Zollfrank, and L. Wondraczek, “Origin of broad NIR photoluminescence in bismuthate glass and Bi-doped glasses at room temperature,” J. Phys. Condens. Matter 21(28), 285106 (2009). [CrossRef] [PubMed]

22

22. S. Khonthon, S. Morimoto, Y. Arai, and Y. Ohishi, “Redox equilibrium and NIR luminescence of Bi2O3-containing glasses,” Opt. Mater. 31(8), 1262–1268 (2009). [CrossRef]

]. So we can confirm that the darking effect of glass 0.5B750 is associated with the reduction of Bi atoms and the precipitation of Bi metallic colloid. And the succeeding color change from back to brown when the temperature rises above 750 °C may be due to the melting of metallic Bi at high temperatures and the subsequent oxidation of Bi atoms into Bi ions. It is obviously that as the heat-treatment temperature increases, the absorption edge of these glasses first red shifts until the temperature reaches 750 °C, then it blue shifts to a large extent again. There are two absorption bands around 500 nm and 700 nm in glass 0.5B, which can be ascribed to the absorption of Bi+ ions [2

2. S. Zhou, N. Jiang, B. Zhu, H. Yang, S. Ye, G. Lakshminarayana, J. Hao, and J. Qiu, “Multifunctional bismuth-doped nanoporous silica glass: from blue-green, orange, red, and white light sources to ultra-broadband infrared amplifiers,” Adv. Funct. Mater. 18(9), 1407–1413 (2008). [CrossRef]

,5

5. J. Ren, G. Dong, S. Xu, R. Bao, and J. Qiu, “Inhomogeneous broadening, luminescence origin and optical amplification in bismuth-doped glass,” J. Phys. Chem. A 112(14), 3036–3039 (2008). [CrossRef] [PubMed]

,23

23. B. Xu, D. Tan, M. Guan, Y. Teng, J. Zhou, J. Qiu, and Z. Hong, “Broadband Near-Infrared Luminescence from γ-ray Irradiated Bismuth-Doped Y4GeO8 Crystals,” J. Electrochem. Soc. 158(9), G203–G206 (2011). [CrossRef]

]. These absorption bands become weak for glass 0.5B690, indicating the decrease of Bi+ ions concentration. No absorption bands are observed in glass 0.5B750. The absorption bands still exist in glass 0.5B810, however, their absorption coefficients are larger than those of glass 0.5B which may be due to the Mie scattering by precipitated nanocrystals in the glass [21

21. G. Lin, D. Tan, F. Luo, D. Chen, Q. Zhao, and J. Qiu, “Linear and nonlinear optical properties of glasses doped with Bi nanoparticles,” J. Non-Cryst. Solids 357(11–13), 2312–2315 (2011). [CrossRef]

], so it is difficult to calculate the intensity of these bands. The temperature-dependent absorption spectra confirms the supposition of the reduction and precipitation of Bi metallic colloid as temperature rises from 670 °C to 750 °C and then melting and oxidation of Bi atoms to Bi ions as temperature rises above 750 °C. The change of Bi in glasses can be expressed as follows:

Bi+[I]Bi0[II]Bimetalliccolloid[III]Bi+
(1)

The processes [I] and [II] have been reported [21

21. G. Lin, D. Tan, F. Luo, D. Chen, Q. Zhao, and J. Qiu, “Linear and nonlinear optical properties of glasses doped with Bi nanoparticles,” J. Non-Cryst. Solids 357(11–13), 2312–2315 (2011). [CrossRef]

,22

22. S. Khonthon, S. Morimoto, Y. Arai, and Y. Ohishi, “Redox equilibrium and NIR luminescence of Bi2O3-containing glasses,” Opt. Mater. 31(8), 1262–1268 (2009). [CrossRef]

], but the process [III] hasn’t been reported before. As shown in Fig. 1, larger concentration of Bi dopant leads to the formation of more Bi metallic colloid. As noble metal particles are often used as nucleation agent in the preparation process of glass-ceramics [24

24. P. Izak, P. Hrma, B. W. Arey, and T. J. Plaisted, “Effect of feed melting, temperature history, and minor component addition on spinel crystallization in high-level waste glass,” J. Non-Cryst. Solids 289(1–3), 17–29 (2001). [CrossRef]

], the Bi metallic colloid here can also act as nucleation agent to promote the nucleation and crystallization. So, lower crystallization onset temperature and maximum crystallization temperature occur in the case of larger concentration of Bi dopant.

Thus, we can understand the relationship between NIR emission intensity and heat-treatment temperature in Fig. 2. In the first stage, as the heat-treatment temperature rises, Bi+ ions are reduced into Bi atoms, then more and more Bi atoms aggregate to form Bi metallic colloids. The decrease of Bi+ ions makes the NIR emission intensity lower. In the second stage, Bi metallic colloids melt and are oxidized into Bi+ ions gradually with the rising of temperature, and the increase of Bi+ ions leads to the increase of NIR emission intensity. In the third stage, Bi metallic colloids continues to melt and be oxidized into Bi+ ions. Furthermore, due to the crystallization, the relative volume of residual glassy phase in glasses decreases as temperature rises. So the concentration of Bi+ ions in the residual glassy phase rises as temperature rises. As shown in Fig. 2(b), the maximum NIR emission intensity occurs when the Bi dopant concentration is 1.0 mol%. Therefore, when the concentration of Bi+ ions in the residual glassy phase is over this concentration, NIR emission intensity begins to decrease due to the concentration quenching effect. As shown in Fig. 2(f)‑(h), owing to the higher Bi dopant concentration in glass 2.0B, compared with glasses 0.5B and 1.0B, more Bi metallic colloid forms at 710 °C, and more Bi+ ions form at 790 °C. So the temperature for the disappearance of NIR luminescence and the reach of the maximal intensity value for glass 2.0B is lower than that of glass 0.5B and 1.0B in the first and second stages, respectively. In the second stage, as a result of concentration quenching, the maximal intensity value is much higher for glass 0.5B (about 80% of the emission intensity for the as-made glass) than glass 1.0B (about 40%) and glass 2.0B (about 10%).

In order to investigate the structural change of the glasses at different Bi dopant concentration and heat-treatment temperatures and further confirm the supposition before, XRD and TEM were performed. Figure 4
Fig. 4 XRD patterns of Bi-doped glasses before and after heat-treatment at various temperatures. The JCPDS card numbers of the crystals MgGeO3 and GeO2 are listed in the figure.
shows XRD patterns of Bi-doped glasses before and after heat-treatment at 710, 750 and 810 °C. The crystallization peaks correspond to the precipitation of MgGeO3 (JCPDS file no. 34-0281), tetragonal GeO2 (JCPDS file no. 73-1306, called GeO2-t, hereafter) and hexagonal GeO2 (JCPDS file no. 36-1463, called GeO2-h, hereafter) nanocrystals. All the diffraction peaks become stronger and sharper when the heat-treatment temperature increases from 710 to 810 °C, indicating the increase of crystallinity. It is observed that glasses 2.0B and 0.5B710 are completely amorphous, while the peaks attributed to MgGeO3 and GeO2-t are observed in glass 2.0B710. Compared with glass 0.5B750, GeO2-h nanocrystals precipitate in glass 2.0B750. It is observed that more MgGeO3, GeO2-t and GeO2-h crystals precipitate in glasses 2.0B750 and 2.0B810 than glasses 0.5B750 and 0.5B810. As shown in Fig. 2, all the crystallization peaks become stronger and sharper with the increase of Bi dopant concentration. It is consistent with the results of Fig. 1 that the increase of Bi dopant leads to the increase of crystallinity. We prepared Bi-doped MgGeO3 and GeO2 crystals, however, no NIR emission is observed in Bi-doped MgGeO3 and GeO2 crystals. So the increase of crystallinity with Bi dopant concentration further confirms the change of Bi in the process [II] of Eq. (1) as temperature rises.

Figure 5
Fig. 5 TEM and HRTEM images of (a) glass 0.5B750, (b)‑(c) glass 2.0B750.
presents TEM and HRTEM images of glasses 0.5B750 and 2.0B750. Few small nanocrystals (4‑7 nm in diameter) are observed in the HRTEM image of glass 0.5B750. However, in accordance with the results of Fig. 4, many small nanocrystals (1.2‑2.7 nm in diameter) precipitate and surround larger ones (12‑22 nm in diameter) in glass 2.0B750, and the distribution density of nanocrystals increases with increasing Bi dopant concentration. These results further confirm the supposition of Eq. (1) and are consistent with the results of Fig. 1 that larger concentration of Bi dopant leads to the formation of more Bi metallic colloid which acts as nucleation agent to promote the nucleation and crystallization in the glasses.

4. Conclusion

In summary, broadband near-infrared photoluminescence in 1.0-1.6µm region was observed from Bi-doped MgO–Al2O3–GeO2 glasses. The NIR luminescence excited at 480, 680 and 800 nm is ascribed to the electronic transition 3P13P0 of Bi+ ions in distinct sites. The NIR emission quenching as heat-treatment temperature rises may be due to the formation of Bi metallic colloids. As the heat-treatment temperature continues going up, Bi metallic colloid melts and are oxidized into Bi+ ions leading to the reviving of NIR emission. Further increases the temperature, concentration quenching of Bi+ ions results in the decrease of NIR emission intensity. The formation of Bi metallic colloid as nucleation agent promotes the nucleation and crystallization of MgGeO3 and GeO2 nanocrystals in glasses. The results help to the design of the fabrication process of Bi-doped optical fiber. These may potentially provide a scientific reference for the control of luminescence properties of main group elements in glasses.

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 50872123, 50802083, 51072054 and 51102209), National Basic Research Program of China (2011CB808100).

References and links

1.

M. Yamada, H. Ono, and Y. Ohishi, “Low-noise, broadband Er3+-doped silica fiber amplifiers,” Electron. Lett. 34(15), 1490–1491 (1998). [CrossRef]

2.

S. Zhou, N. Jiang, B. Zhu, H. Yang, S. Ye, G. Lakshminarayana, J. Hao, and J. Qiu, “Multifunctional bismuth-doped nanoporous silica glass: from blue-green, orange, red, and white light sources to ultra-broadband infrared amplifiers,” Adv. Funct. Mater. 18(9), 1407–1413 (2008). [CrossRef]

3.

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5.

J. Ren, G. Dong, S. Xu, R. Bao, and J. Qiu, “Inhomogeneous broadening, luminescence origin and optical amplification in bismuth-doped glass,” J. Phys. Chem. A 112(14), 3036–3039 (2008). [CrossRef] [PubMed]

6.

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I. A. Bufetov and E. M. Dianov, “Bi-doped fiber lasers,” Laser Phys. Lett. 6(7), 487–504 (2009). [CrossRef]

10.

V. V. Dvoyrin, V. M. Mashinsky, L. I. Bulatov, I. A. Bufetov, A. V. Shubin, M. A. Melkumov, E. F. Kustov, E. M. Dianov, A. A. Umnikov, V. F. Khopin, M. V. Yashkov, and A. N. Guryanov, “Bismuth-doped-glass optical fibers-a new active medium for lasers and amplifiers,” Opt. Lett. 31(20), 2966–2968 (2006). [CrossRef] [PubMed]

11.

I. A. Bufetov, K. M. Golant, S. V. Firstov, A. V. Kholodkov, A. V. Shubin, and E. M. Dianov, “Bismuth activated alumosilicate optical fibers fabricated by surface-plasma chemical vapor deposition technology,” Appl. Opt. 47(27), 4940–4944 (2008). [CrossRef] [PubMed]

12.

I. A. Bufetov, S. V. Firstov, V. F. Khopin, O. I. Medvedkov, A. N. Guryanov, and E. M. Dianov, “Bi-doped fiber lasers and amplifiers for a spectral region of 1300-1470 nm,” Opt. Lett. 33(19), 2227–2229 (2008). [CrossRef] [PubMed]

13.

I. Razdobreev, L. Bigot, V. Pureur, A. Favre, G. Bouwmans, and M. Douay, “Efficient all-fiber bismuth-doped laser,” Appl. Phys. Lett. 90(3), 031103 (2007). [CrossRef]

14.

V. V. Dvoyrin, V. M. Mashinsky, and E. M. Dianov, “Yb-Bi pulsed fiber lasers,” Opt. Lett. 32(5), 451–453 (2007). [CrossRef] [PubMed]

15.

N. D. Psaila, R. R. Thomson, H. T. Bookey, A. K. Kar, N. Chiodo, R. Osellame, G. Cerullo, G. Brown, A. Jha, and S. Shen, “Femtosecond laser inscription of optical waveguides in Bismuth ion doped glass,” Opt. Express 14(22), 10452–10459 (2006). [CrossRef] [PubMed]

16.

B. Zhou, H. Lin, B. Chen, and E. Y. B. Pun, “Superbroadband near-infrared emission in Tm-Bi codoped sodium-germanium-gallate glasses,” Opt. Express 19(7), 6514–6523 (2011). [CrossRef] [PubMed]

17.

V. G. Truong, L. Bigot, A. Lerouge, M. Douay, and I. Razdobreev, “Study of thermal stability and luminescence quenching properties of bismuth-doped silicate glasses for fiber laser applications,” Appl. Phys. Lett. 92(4), 041908 (2008). [CrossRef]

18.

L. Le Neindre, S. Jiang, B. Hwang, T. Luo, J. Watson, and N. Peyghambarian, “Effect of relative alkali content on absorption linewidth in erbium-doped tellurite glasses,” J. Non-Cryst. Solids 255(1), 97–102 (1999). [CrossRef]

19.

S. Zhou, H. Dong, H. Zeng, J. Hao, J. Chen, and J. Qiu, “Infrared luminescence and amplification properties of Bi-doped GeO2−Ga2O3−Al2O3 glasses,” J. Appl. Phys. 103(10), 103532 (2008). [CrossRef]

20.

M. Peng, C. Zollfrank, and L. Wondraczek, “Origin of broad NIR photoluminescence in bismuthate glass and Bi-doped glasses at room temperature,” J. Phys. Condens. Matter 21(28), 285106 (2009). [CrossRef] [PubMed]

21.

G. Lin, D. Tan, F. Luo, D. Chen, Q. Zhao, and J. Qiu, “Linear and nonlinear optical properties of glasses doped with Bi nanoparticles,” J. Non-Cryst. Solids 357(11–13), 2312–2315 (2011). [CrossRef]

22.

S. Khonthon, S. Morimoto, Y. Arai, and Y. Ohishi, “Redox equilibrium and NIR luminescence of Bi2O3-containing glasses,” Opt. Mater. 31(8), 1262–1268 (2009). [CrossRef]

23.

B. Xu, D. Tan, M. Guan, Y. Teng, J. Zhou, J. Qiu, and Z. Hong, “Broadband Near-Infrared Luminescence from γ-ray Irradiated Bismuth-Doped Y4GeO8 Crystals,” J. Electrochem. Soc. 158(9), G203–G206 (2011). [CrossRef]

24.

P. Izak, P. Hrma, B. W. Arey, and T. J. Plaisted, “Effect of feed melting, temperature history, and minor component addition on spinel crystallization in high-level waste glass,” J. Non-Cryst. Solids 289(1–3), 17–29 (2001). [CrossRef]

OCIS Codes
(060.2280) Fiber optics and optical communications : Fiber design and fabrication
(160.2540) Materials : Fluorescent and luminescent materials
(160.4670) Materials : Optical materials
(160.4760) Materials : Optical properties

ToC Category:
Materials

History
Original Manuscript: August 19, 2011
Revised Manuscript: October 9, 2011
Manuscript Accepted: October 12, 2011
Published: November 2, 2011

Citation
Beibei Xu, Shifeng Zhou, Miaojia Guan, Dezhi Tan, Yu Teng, Jiajia Zhou, Zhijun Ma, Zhanglian Hong, and Jianrong Qiu, "Unusual luminescence quenching and reviving behavior of Bi-doped germanate glasses," Opt. Express 19, 23436-23443 (2011)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-19-23-23436


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References

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  3. X. G. Meng, J. R. Qiu, M. Y. Peng, D. P. Chen, Q. Z. Zhao, X. W. Jiang, and C. S. Zhu, “Infrared broadband emission of bismuth-doped barium-aluminum-borate glasses,” Opt. Express13(5), 1635–1642 (2005). [CrossRef] [PubMed]
  4. M. Peng, J. Qiu, D. Chen, X. Meng, and C. Zhu, “Superbroadband 1310 nm emission from bismuth and tantalum codoped germanium oxide glasses,” Opt. Lett.30(18), 2433–2435 (2005). [CrossRef] [PubMed]
  5. J. Ren, G. Dong, S. Xu, R. Bao, and J. Qiu, “Inhomogeneous broadening, luminescence origin and optical amplification in bismuth-doped glass,” J. Phys. Chem. A112(14), 3036–3039 (2008). [CrossRef] [PubMed]
  6. S. Zhou, H. Dong, H. Zeng, G. Feng, H. Yang, B. Zhu, and J. Qiu, “Broadband optical amplification in Bi-doped germanium silicate glass,” Appl. Phys. Lett.91(6), 061919 (2007). [CrossRef]
  7. J. Ren, J. Qiu, B. Wu, and D. Chen, “Ultrabroad infrared luminescences from Bi-doped alkaline earth metal germanate glasses,” J. Mater. Res.22(06), 1574–1578 (2007). [CrossRef]
  8. M. Peng, J. Qiu, D. Chen, X. Meng, I. Yang, X. Jiang, and C. Zhu, “Bismuth- and aluminum-codoped germanium oxide glasses for super-broadband optical amplification,” Opt. Lett.29(17), 1998–2000 (2004). [CrossRef] [PubMed]
  9. I. A. Bufetov and E. M. Dianov, “Bi-doped fiber lasers,” Laser Phys. Lett.6(7), 487–504 (2009). [CrossRef]
  10. V. V. Dvoyrin, V. M. Mashinsky, L. I. Bulatov, I. A. Bufetov, A. V. Shubin, M. A. Melkumov, E. F. Kustov, E. M. Dianov, A. A. Umnikov, V. F. Khopin, M. V. Yashkov, and A. N. Guryanov, “Bismuth-doped-glass optical fibers-a new active medium for lasers and amplifiers,” Opt. Lett.31(20), 2966–2968 (2006). [CrossRef] [PubMed]
  11. I. A. Bufetov, K. M. Golant, S. V. Firstov, A. V. Kholodkov, A. V. Shubin, and E. M. Dianov, “Bismuth activated alumosilicate optical fibers fabricated by surface-plasma chemical vapor deposition technology,” Appl. Opt.47(27), 4940–4944 (2008). [CrossRef] [PubMed]
  12. I. A. Bufetov, S. V. Firstov, V. F. Khopin, O. I. Medvedkov, A. N. Guryanov, and E. M. Dianov, “Bi-doped fiber lasers and amplifiers for a spectral region of 1300-1470 nm,” Opt. Lett.33(19), 2227–2229 (2008). [CrossRef] [PubMed]
  13. I. Razdobreev, L. Bigot, V. Pureur, A. Favre, G. Bouwmans, and M. Douay, “Efficient all-fiber bismuth-doped laser,” Appl. Phys. Lett.90(3), 031103 (2007). [CrossRef]
  14. V. V. Dvoyrin, V. M. Mashinsky, and E. M. Dianov, “Yb-Bi pulsed fiber lasers,” Opt. Lett.32(5), 451–453 (2007). [CrossRef] [PubMed]
  15. N. D. Psaila, R. R. Thomson, H. T. Bookey, A. K. Kar, N. Chiodo, R. Osellame, G. Cerullo, G. Brown, A. Jha, and S. Shen, “Femtosecond laser inscription of optical waveguides in Bismuth ion doped glass,” Opt. Express14(22), 10452–10459 (2006). [CrossRef] [PubMed]
  16. B. Zhou, H. Lin, B. Chen, and E. Y. B. Pun, “Superbroadband near-infrared emission in Tm-Bi codoped sodium-germanium-gallate glasses,” Opt. Express19(7), 6514–6523 (2011). [CrossRef] [PubMed]
  17. V. G. Truong, L. Bigot, A. Lerouge, M. Douay, and I. Razdobreev, “Study of thermal stability and luminescence quenching properties of bismuth-doped silicate glasses for fiber laser applications,” Appl. Phys. Lett.92(4), 041908 (2008). [CrossRef]
  18. L. Le Neindre, S. Jiang, B. Hwang, T. Luo, J. Watson, and N. Peyghambarian, “Effect of relative alkali content on absorption linewidth in erbium-doped tellurite glasses,” J. Non-Cryst. Solids255(1), 97–102 (1999). [CrossRef]
  19. S. Zhou, H. Dong, H. Zeng, J. Hao, J. Chen, and J. Qiu, “Infrared luminescence and amplification properties of Bi-doped GeO2−Ga2O3−Al2O3 glasses,” J. Appl. Phys.103(10), 103532 (2008). [CrossRef]
  20. M. Peng, C. Zollfrank, and L. Wondraczek, “Origin of broad NIR photoluminescence in bismuthate glass and Bi-doped glasses at room temperature,” J. Phys. Condens. Matter21(28), 285106 (2009). [CrossRef] [PubMed]
  21. G. Lin, D. Tan, F. Luo, D. Chen, Q. Zhao, and J. Qiu, “Linear and nonlinear optical properties of glasses doped with Bi nanoparticles,” J. Non-Cryst. Solids357(11–13), 2312–2315 (2011). [CrossRef]
  22. S. Khonthon, S. Morimoto, Y. Arai, and Y. Ohishi, “Redox equilibrium and NIR luminescence of Bi2O3-containing glasses,” Opt. Mater.31(8), 1262–1268 (2009). [CrossRef]
  23. B. Xu, D. Tan, M. Guan, Y. Teng, J. Zhou, J. Qiu, and Z. Hong, “Broadband Near-Infrared Luminescence from γ-ray Irradiated Bismuth-Doped Y4GeO8 Crystals,” J. Electrochem. Soc.158(9), G203–G206 (2011). [CrossRef]
  24. P. Izak, P. Hrma, B. W. Arey, and T. J. Plaisted, “Effect of feed melting, temperature history, and minor component addition on spinel crystallization in high-level waste glass,” J. Non-Cryst. Solids289(1–3), 17–29 (2001). [CrossRef]

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