Journal of The Electrochemical Society, 158 (7) G151-G154 (2011)

C 0013-4651/2011/158(7)/G151/4/$28.00 V The Electrochemical Society

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Abnormal Luminescence Behavior in Bi-Doped Borosilicate Glasses

Miaojia Guan,a Xi Wang,b Yixi Zhuang,b Geng Lin,c Junhua Xie,a Morten Mattrup Smedskjr,d and Jianrong Qiua,z
State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, China Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan State Key Laboratory of High Field Laser Physics, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800, China d Section of Chemistry, Aalborg University, DK-9000 Aalborg, Denmark
b c a

We report on the visible and near-infrared luminescence properties of Bi-doped sodium borosilicate glasses. The emission intensity at 420 nm due to the transition of Bi3 decreases with increasing B2O3 concentration. Boron anomaly features were observed in both the visible emission at 618 nm due to the transition of Bi2 and the near-infrared emission at 1340 nm due to the transition of Bi. We have proposed a mechanism that suggests Bi to be responsible for the near-infrared luminescence, and [BO4] units play an important role for stabilizing Bi ions with low valence state in glasses. C V 2011 The Electrochemical Society. [DOI: 10.1149/1.3586039] All rights reserved. Manuscript submitted January 25, 2011; revised manuscript received April 8, 2011. Published May 2, 2011.

In order to develop tunable lasers and broadband ber ampliers for the efcient wavelength division multiplexing technology, it is necessary to explore and synthesize new luminescent materials with broader band for optical gain in the telecommunication wavelength region, especially at 1300 and 1550 nm. Recently, it has been discovered that Bi-doped glasses are promising candidates as tunable laser or broadband optical amplier materials because these glasses exhibit broadband near-infrared (NIR) luminescence covering the 11001600 nm wavelength region.15 In addition, laser oscillation was recently obtained in the spectral region between 1150 and 1300 nm from Bi-doped alumino silicate ber.6,7 However, the luminescent center responsible for the NIR luminescence has not been clearly identied up to now. The ternary Na2O-B2O3-SiO2 system forms the basis for a number of glasses of considerable technological importance. For example these glasses are used as optical lens, ovenwares, nuclear waste materials and in the electronics industry. A considerable amount of results have been obtained about the structure and properties of these glasses.8,9 The properties of the glasses depend on their microstructure and network topology, which are governed by competitive network formation of the various silicate and borate structural groups. It is well known that the luminescent properties of Bi-doped glasses depend on the host glass composition and its micro-structure. In this paper, we use sodium borosilicate glasses as the matrix and study the relationship between the luminescent property and host glass composition. For the rst time, we observed visible and NIR luminescence with boron anomaly feature in Bi doped sodium borosilicate glasses. The luminescence mechanism is discussed based on the relationship between glass composition and glass microstructure. Experimental Glass compositions (in mol%) of xB2O3-(30-x)Na2O-69SiO21Bi2O3 (x 5, 10, 13, 15, 16.5, 20, 23, and 25) were studied and notated as Gn (n 18), respectively. The glass samples were prepared by the conventional melting-quenching method. Analytical reagents Na2CO3, H3BO3, SiO2, and Bi2O3 were used as raw materials. Approximately 25 g batches were mixed homogenously in an agate mortar and melted in a corundum crucible. The melting was carried out at 1520 C for 45 min under ambient atmosphere. The melts were then cast and quenched on a pre-heated iron plate. The samples were cut into sizes of 10 10 1.6 mm3 and polished for optical measurements.
z

The luminescence spectra and the uorescence decay curves in both visible and NIR regions were recorded using an FLS920 uorescence spectrophotometer (Edinburgh Instrument Ltd., U.K.). All of the measurements were carried out at room temperature. Results and Discussion Figures 1a1c show the excitation and emission spectra of the G1, G5, and G8 samples respectively. A blue emission is observed around 420 nm in sample G1 when this glass is excited at 312 nm. It can be attributed to the electronic transition 3P1 !1S0 of Bi3.1013 The blue emission at 420 nm is also observed in G5, together with an emission band centered at 618 nm due to the electronic transition 2 P3/2 ! 2P1/2 of Bi2 under 468 nm excitation.14,15 In contrast, only emission at 618 nm can be detected in sample G8 i.e., no blue emission at 420 nm was observed in this sample. The visible luminescence spectra of Bi doped glasses with different x values are shown in Figs. 2a and 2b. Under 312 nm excitation, the samples show intense blue luminescence centered at 420 nm (Fig. 2a). Comparison of the luminescence spectra of the glasses with different Na2O concentration, we clearly observed that the emission intensity at 420 nm decreases with decreasing Na2O concentration (or increasing B2O3 concentration). This may be due to the change in optical basicity of the glasses since the lower optical basicity favors the formation of lower valence state for the polyvalent metal ions.16 The theoretical optical basicity (Kth) for the glass system under study was calculated using the Eq. 1 Kth X1K1 X2K2 X3K3 XnKn [1]

E-mail: qjr@zju.edu.cn

where Kn is the optical basicity quantity of the oxide n and Xn is the proportion of oxygen atoms that the oxide n contributes. The optical basicity values Kn are taken from Ref. 17. The values of Kth with different B2O3 concentration are shown in Table I. Figure 3 shows the relationship between the emission intensity at 420 nm and the optical basicity of the host composition. The decrease in Kth agrees well with the decrease of the emission intensity at 420 nm under 312 nm excitation. This result indicates that the extent of reduction of Bi3 ions to lower valence state bismuth ions (such as Bi2, Bi) increases with increasing B2O3 concentration. Figure 2b shows the luminescence spectra of glass samples excited at 468 nm. In samples G1 and G2, we only observe a weak band at 520 nm, from the excitation spectra of sample G1 (see Fig. 1), we can observe that the excitation band corresponding to the 520 nm emission is similar to the one of the 420 nm emission. So we infer that the emission at 520 nm maybe come from the 3P1 ! 1S0 transition of Bi3. With the increase of B2O3 concentration, a new emission band at 618 nm emerges in the emission spectra of the

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Journal of The Electrochemical Society, 158 (7) G151-G154 (2011)

Table I. Values of K, ratio of tetrahedral to total boron (N4) and [BO4] for each glass composition. Sample G1 G2 G3 G4 G5 G6 G7 G8
a

B2O3(mol %) 5 10 13 15 16.5 20 23 25

K 0.5918 0.5730 0.5609 0.5533 0.5479 0.5261 0.5069 0.4946

N4 a 1.000 0.897 0.813 0.778 0.759 0.500 0.304 0.200

[BO4](mol %) 10.00 17.94 21.14 23.34 25.04 20.00 13.98 10.00

N4 are calculated by Bray model.8

Figure 1. (Color online) Excitation and emission spectra of (a) G1, (b) G5, and (c) G8 in the visible region. The solid lines and dashed lines are the emission and excitation spectra, respectively.

samples G3 to G8. Different from the blue emission band at 420 nm from Bi3, the red emission intensity increases with increasing B2O3 concentration from 5 to 16.5 mol % B2O3, and then decreases with further increase of B2O3 concentration. In Fig. 2b, we also

observe a weak emission band at 780 nm, which has been reported in many silicate glasses.18 The dependence of the 618 nm emission intensity on optical basicity of the glass samples is shown in Fig. 3. We have also performed uorescence decay measurements for sample G5 excited at 312 and 468 nm (see insets of Figs. 2a2b). The monitoring wavelengths were 420 and 618 nm, and the estimated lifetimes are about 2.8 s (at 420 nm) and 3.6 s (at 618 nm). These values are similar to the lifetimes of the Bi3 and Bi2 centers in crystal hosts, respectively.11,14 Figure 4a shows the NIR emission spectra of the glass samples excited by 808 nm laser diode (LD). The decay curve of the 1340 nm emission for glass sample G5 at room temperature is presented in the inset of Fig. 4a, and the estimated lifetime is 365 s. It is interesting that the emission intensity increases from sample G1 to G5, and then decreases from sample G5 to G8. Sample G5 shows the highest emission intensity, similar to the red emission from Bi2 (Fig. 2b). Many reports have shown that decrease of the optical basicity of glass results in the increase of the near-infrared emission intensity for Bi-doped glasses.3,4 As mentioned above, Bi3 ions are reduced to lower valence state bismuth ions with the decrease of the optical basicity of glass. Thus, the red emission or near-infrared emission intensity may increase with increasing B2O3 concentration. However as shown in Figs. 3 and 4, both the intensities of visible emission at 618 nm and near-infrared emission at 1340 nm show a maximum at x 16.5 (sample G5). These phenomena are unusual in Bi doped glasses since usually both the intensities of visible emission at 618 nm and near-infrared emission at 1340 nm increase with decreasing optical basicity. The ratio of four-coordinated to three-coordinated boron in borate glasses depends on the concentration of network modiers, which causes many physical and chemical properties to vary

Figure 2. (Color online) Emission spectra of the samples (a) 312 nm excited, the inset shows the uorescence decay curve of sample G5 (monitoring wavelength is 420 nm). (b) 468 nm excited, the inset shows the uorescence decay curve of sample G5 (monitoring wavelength is 618 nm).

Figure 3. (Color online) Dependence of the 420 and 618 nm emission intensities on the optical basicity of the glass samples.

Journal of The Electrochemical Society, 158 (7) G151-G154 (2011)

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Figure 5. (Color online) NIR luminescence spectra of the samples excited at 468 nm.

Figure 4. (Color online) (a) NIR emission spectra of the samples excited at 808 nm LD. The inset shows NIR uorescence decay curves of sample G5 (monitoring wavelength is 1340 nm and the corresponding excitation wavelength is 808 nm). (b) Dependence of NIR emission intensity at 1340 nm and [BO4]% content of the related glasses on B2O3 mol %.

nonmonotonically with composition. This effect has been termed the boron anomaly by glass scientists.19,20 Munoz et al.21 reported a nonmonotonical behaviour of the glass properties of lithium borophosphate glasses, which is interpreted in terms of boron anomaly, and the boron anomaly occurs when [BO4] tetrahedrons transform into [BO3] trigonal units after B2O3 substitutes for P2O5. The relationship between boron anomaly features and glass micro-structure in sodium borosilicate glasses has also been investigated thoroughly. The structure of the sodium borosilicate glasses is governed by the ratios R and K, where R is the molar ratio Na2O/B2O3, and K is the molar ratio SiO2/B2O3.22 Here we use a model presented by Bray et al.,8 which has been successfully applied to describe a number of 11 B NMR data, to calculate N4 (dened as the ratio between [BO4] units and total amount of borate units) of our glass samples. It indicates that for R<Rmax (Rmax is the R value corresponding to maximum N4 value, Rmax 0.5 K/16), all of Na2O is consumed to form [BO4] units and therefore N4 R; For RRmax, N4 N4max 0.25 (R Rmax)/(1 K), the silicate and borate network are mixed together to form structural groups in which boron tetrahedrons are bridged to four silica tetrahedral. The N4 values obtained by using the Bray model are given in Table I. The related concentration of [BO4] ([BO4]% B2O3% N4) was also given in Table I. The result shows that the N4 values decrease with increasing B2O3 concentration, which means the boron coordination has changed from [BO4] to [BO3]. The increase in the boron content is reected in the increasing of the amount of [BO3] trigonal units, the proportion of [BO3] units increases to 80% of the total amount of borate units when 25% B2O3 was added. And the total amount of [BO4] units shows a maximum at x 16.5.

As shown in Fig. 4b, the intensity of the NIR emission at 1340 nm shows the same dependence on B2O3 concentration as does the concentration of [BO4] units. Therefore, we infer that [BO4] unit plays an important role for the NIR luminescence center (here we label it as Bix). Since each [BO4] unit possesses a negative charge, an alkali cation or other metallic cation is required to charge compensate the [BO4] unit. In the sodium borosilicate glasses, Na and Bix may locate near the [BO4] unit for charge compensation. The valence electrons of Bi are lack of shielding from surrounding crystal elds, i.e., electrostatic interactions could occur between Bi cation and neighboring [BO4] unit. The [BO4] units are considered to play an electrontransferring role in the reduction process of Eu3 ! Eu2 in the nonreducing atmosphere.23 The three-dimensional network of [BO4] tetrahedral acts as a shield; it can isolate Eu2 ions from each other and completely or partly surround Eu2 ions and resist the attack of oxygen. Therefore Eu2 ions can retain the divalent state in air. Here the existence of [BO4] unit may have the same effect on Bi. It is expected that more bismuth with lower valence state will be created with the increase of the number of [BO4] units in the glass samples, i.e., an increasing number of Bi2 and Bix ions can stably exist in glass with increasing concentration of [BO4] units in the glasses. So far the origin of the NIR luminescence in Bi-doped glasses remains controversial and unclear. There have been many conicting evidences as to whether the lower valence Bi species or the higher valence Bi species contributes to the NIR luminescence.1,4 The fact that both the red emission and the near-infrared emission exhibit the similar boron anomaly feature indicated that they may arise from the same active-center, viz., the NIR emission may be ascribed to Bi2. However, the uorescence decay time of the NIR emission is 2 order of magnitude longer than that of Bi2. Therefore, it should be ascribed to another type of active center. According to analysis presented, the decrease of optical basicity and increase of the number of [BO4] unit favor the formation of bismuth ions with lower valence state. Therefore the NIR emission may be attributed to low valence state Bi, most probably Bi considering the effects of glass matrix and charge compensation, rather than a higher valence state. Figure 5 shows the NIR emission spectra of the glass samples excited at 468 nm. There are two main emission bands at 1154 and 1266 nm. The gap in the emission band at wavelengths between 1350 and 1400 nm should be ascribed to absorption of OH related to spectroscopic measurement system. The results show that the peak position of the broadband NIR emission shifts from 1266 to 1154 nm when the B2O3 concentration from 5 to 25 mol %. The emission intensity shows the same boron anomaly feature as discussed above. The NIR emission band can be deconvoluted into two

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Journal of The Electrochemical Society, 158 (7) G151-G154 (2011) References

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bands, one at 1266 nm, and another one at 1154 nm. These bands may be related to Bi located near [BO4]-Si ([BO4] unit connected with [SiO4] units) and [BO4]-B ([BO4] unit connected with [BO3] units) glass network, respectively. Hence, this phenomenon can also be attributed to the structural change of the sodium borosilicate glasses. Furthermore, it suggests that we can obtain broad tunable NIR emission by adjusting B2O3 concentration. Conclusion In conclusion, we have studied the composition dependence of the luminescence properties of bismuth-doped sodium borosilicate glasses. We have found that both the visible and NIR emissions vary nonmonotonically with the [B2O3]/[Na2O] ratio, which is ascribed to the so-called boron anomaly. The number of [BO4] units play an important role for the luminescence of bismuth ions with low valence state. Furthermore we nd that the infrared emission is quite sensitive to glass composition and excitation wavelength. Our ndings suggest that the NIR luminescence in Bi-doped glasses originates from a lower valence state Bi ion, most likely from Bi. Acknowledgment This work was nancially supported by the National Natural Science Foundation of China (Grant Nos. 51072054, 50872123, and 50802083) and the National Basic Research Program of China (2011CB808100).