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Luminescence of Nd3+- Doped Bi2O3-B2O3 Glass System
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Procedia Engineering
ProcediaProcedia Engineering 00 (2012) 000–000 Engineering 32 (2012) 827 – 832 www.elsevier.com/locate/procedia
I-SEEC2011
Luminescence of Nd3+- Doped Bi2O3-B2O3 Glass System K. Boonina,d∗ J. Kaewkhaob,d, N. Nuntawongc, P. Limsuwana,d a
Department of Physics, Faculty of Science,King Mongkut’s University of Technology Thonburi, Bangkok, Thailand, 10140 b Center of Excellence in Glass Technology and Materials Science, Nakhon Pathom Rajabhat University, Nakorn Pathom, Thailand 73000 c Photonic Technology Laboratory, National Electronics and Computer Technology Center, Pathumthani 12120, Thailand d Thailand Center of Excellence in Physics, CHE, Ministry of Education, Bangkok 10400, Thailand Elsevier use only: Received 30 September 2011; Revised 10 November 2011; Accepted 25 November 2011.
Abstract Absorption and luminescence properties of Nd3+ in B2O3-Bi2O3 glass system with composition xNd2O3:(70x)B2O3:30Bi2O3 are measured for the composition range 0≤x≤2.5 (in mol%). The glasses were prepared by normal melt-quench technique and investigated their optical and photoluminescence properties. From uv-visble spectrophotometer data, the various spectroscopic transitions observed are as follows: 4F3/2 (877 nm), 4F5/2 + 2H9/2 (803 nm), 4S3/2 + 4F7/2 (745 nm), 4F9/2 (684 nm), 2H11/2, (630 nm) 4G5/2 + 2G7/2(583 nm), 2K13/2 + 4G7/2 (526nm) 4G9/2 (519 nm) ← 4I9/2. The emission band at 900 1064 and 1336 nm arising from the transition 4F3/2→4I9/2, 4F3/2→4I11/2 and 4F3/2→4I13/2 respectively were observed when the sample was excited by lasers working at 750 nm. All intensity are increases with increasing of Nd2O3 concentration.
© 2010 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of I-SEEC2011 Keywords: Bismuth borate glass; Optical transmission spectra; Luminescence
1. Introduction Rare-earth doped bismuth borate glasses represent a group of materials that provide new opportunities for applications in ber-amplier and mid-infrared laser devices [1]. Compared with other glass hosts, bismuth borate glasses have some unique properties, as they typically possess a high refractive index. As a result, a large stimulated emission cross section and a low nonradiative relaxation rate [2] can be expected, which enhances the probabilities of observing new uorescent emission that is normally quenched in oxide glasses. This makes bismuth borate glasses extremely attractive as host materials for rare-earth ions [3]. In addition, because of their good chemical durabilities and good glass-forming * Corresponding author. E-mail address: [email protected].
1877-7058 © 2012 Published by Elsevier Ltd. doi:10.1016/j.proeng.2012.02.019
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K. Boonin / Procedia Engineering 32 (2012) 827 – 832 K. Boonin et al.et/ al. Procedia Engineering 00 (2012) 000–000
abilities,bismuth borate glasses that have been doped with rare-earth ions show promise as ber amplier and ber oscillator materials. Nd3+ was the rst ion considered for ber-amplier and mid-infrared laser devices because it has a well-known four-level 4F3/2→4I9/2, 4F3/2→4I11/2, 4F3/2→4I13/2 and 4F3/2→4I15/2 transition. In this paper, the Nd3+ doped bismuth borate glasses with composition of 30Bi2O3:(100x)B2O3:xNd2O3 were investigated. The optical and photo luminescence properties change in bismuth borate glasses which containing difference Nd2O3 concentration. Nomenclature UV
Ultraviolet
VIS
Visible
NIR
Near Infrared luminescence
FWHM Full width at half maximum 2. Experimental The glass samples were prepared by using high purity Bi2O3, H3BO3 and Nd2O3 in the composition range of 30Bi2O3:(100-x)B2O3 :xNd2O3 where x = 0.0, 0.5, 1.0, 1.5, 2.0 and 2.5 mol%. Each batch weight about 20 g was melt in high alumina crucible by placing them in an electrical furnace for an hour, at 1,100 °C till a bubble free liquid was formed. These melts were quenched at room temperature in air by pouring between the melt on a stainless steel plate and pressing with another stainless steel plate. The quenched glasses were annealed at 450°C for 3 hour for reduce thermal stress [4], and cool down to the room temperature. All glass samples were cut and polish in proper shape for further studies. The absorption spectra were measured by UV-VIS-NIR spectrophotometer (Shimadzu UV-3100, JAPAN) with a spectral range from 200 to 2000 nm. Near infrared emission spectra were measured with a Quanta Master 3 luminescence spectrometer from Photon Technology International (PTI), using 750 nm excited radiation from a Xenon compact arc lamps. All the measurements were carried out at room temperature. 3. Results and discussions Absorption spectra of Nd3+ doped in bismuth borate glasses are shown in Fig. 1. The optical absorption edges are not sharply defined in glass samples under study, in accordance with their amorphous nature [5]. It can be seen that the transition energy levels vary with the Nd2O3 concentration and depend on covalency and the asymmetry of Nd-O local structure among these host matrices [6]. It is observed that the absorption intensity of the observed bands increase with the increase of Nd2O3 concentration. The absorption bands of Nd3+ correspond to transitions from the 4I9/2 ground state to various excited levels. These transitions were assigned by comparing the band positions in the absorption spectra with a standard wavelength chart for the Nd3+ ion [7]. The various spectroscopic transitions observed are as follows: 4F3/2 (877 nm), 4F5/2 + 2H9/2 (803 nm), 4S3/2 + 4F7/2 (745 nm), 4F9/2 (684 nm), 2 H11/2, (630 nm) 4G5/2 + 2G7/2(583 nm), 2K13/2 + 4G7/2 (526nm) 4G9/2 (519 nm) ← 4I9/2. Moreover, the absorption bands corresponding to 2D3/2, 2G9/2, 4G11/2, 2P1/2 ← 4I9/2 transitions were not clearly observed for the bismuth borate glass.
K.K. Boonin et et al.al. / Procedia Engineering 3200 (2012) 827 – 832 Boonin / Procedia Engineering (2012) 000–000
Fig. 1. Optical absorption spectra of Bi2O3-B2O3-Nd2O3 glass system
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Fig. 2. 900 nm emission spectra of Nd3+ ions in bismuth borate glass samples of different compositions (Bi2O3 content indicated at the right side of the spectra). Pump wavelength was 750 nm
Fig. 3. 1.064 μm emission spectra of Nd3+ ions in bismuth borate glass samples of different compositions (Bi2O3 content indicated at the right side of the spectra). Pump wavelength was 750 nm
K.K.Boonin – 832 Booninetetal.al./ Procedia / ProcediaEngineering Engineering3200(2012) (2012)827 000–000
Fig. 4. 1.336 μm emission spectra of Nd3+ ions in bismuth borate glass samples of different compositions (Bi2O3 content indicated at the right side of the spectra). Pump wavelength was 750 nm
Of the many rare-earth ions, Nd3+ is well known for its favorable characteristics for laser transition[2]. the levels denoted 4F5/2 can be used to absorb light from a pumping source at about 800 nm. Ions excited into the pump band decay, usually nonradiatively, to the upper laser level 4F5/2 in a time that is short in comparison with its radiative lifetime (typically 300 - 600 s)[2]. From this upper laser level 4F3/2 there are four laser transitions 4I15/2 (1.80 μm), 4I13/2 (1.35 μm), 4I11/2 (1.06 μm), and 4I9/2 (0.88 μm). Fig. 2, 3 and 4 exhibit the NIR emission spectrum of samples when pumped by laser at 750 nm. Strong emission band with the center wavelength 0.9, 1.064 and 1.336 μm arising from the transition 4 F3/2→4I9/2, 4F3/2→4I11/2 and 4F3/2→4I13/2 respectively and the full width at half maximum (FWHM) were estimated to be about 52, 44 and 46 nm respectively. The composition dependence of the emission spectra as shown in Fig. 2, 3 and 4. Low Nd2O3 content favors comparably narrower spectra, increasing Nd2O3 content leads to broad. 3. Conclusions In this research, glasses from the system 30Bi2O3:(70-x)B2O3:xNd2O3 (x= 0.0, 0.5, 1.0, 1.5, 2.0, 2.5 mol%) were prepared by melt quenching technique. The absorption peaks at 4F3/2 (877 nm), 4F5/2 + 2H9/2 (803 nm), 4S3/2 + 4F7/2 (745 nm), 4F9/2 (684 nm), 2H11/2, (630 nm) 4G5/2 + 2G7/2(583 nm), 2K13/2 + 4G7/2 (526nm) 4G9/2 (519 nm) of Nd2O3 in bismuth borate glasses were observed. The emission band at 0.9, 1.064 and 1.336 µm arising from the transition 4F3/2→4I9/2, 4F3/2→4I11/2 and 4F3/2→4I13/2 respectively were observed when the sample was excited by lasers working at 750 nm. All intensity are increases with increasing of Er2O3 concentration. The red shift, found for increasing Er2O3 content in the peak wave length of the band.
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K. Boonin / Procedia Engineering 32 (2012) 827 – 832 K. Boonin et al.et/ al. Procedia Engineering 00 (2012) 000–000
Acknowledgements The authors wish to thank National Research Council of Thailand (NRCT) funding this research. Thanks are also due to Research and Development Institute, NPRU for facilities. P. Limsuwan wish to thank commission of Higher Education (NRU Project) for financial support. 6. References [1] Little G. Lakshminarayana, R . Vidya Sagar, S. Buddhudu. NIR luminescence from Er3+/Yb3+,Tm3+/Yb3+,Er3+/Tm3+ and Nd3+ ions-doped zincborotellurite glasses for optical amplication. J. Luminescence 2008; 128: 690-695. [2] M. Yamane, Y. Asahara, Glass for photonic. London, England: THE PRESS SYNDICATE OF THE UNIVERSITY OF CAMBRIDGE; 2004. [3] Y. Q. Qiu, J. Kang, C. X. Li, X. Y. Dong, C.L. Zhao. Broadband NearInfrared Luminescence in Bismuth Borate Glasses. Laser Physics 2010; 20: 487–492. [4] A. Thulasiramudu, S. Budduhudu. . J. Quant. Spec. Radiat. Trans 2006. 97: p.181 [5] B. Eraiah, Sudha G. Bhat. Optical properties of samarium doped zinc–phosphate glasses. J. of Phy. Chem. of Sol 2007. 68: 581-585. [6] B. Karthikeyana, S. Mohanb, M.L. Baesso. . Physica B 2003. 337: 249. [7] G.H. Dieke. Spectra and Energy Levels of Rare-Earth Ions in Crystals. New York: John Wiley & sons; 1969.
Procedia Engineering
ProcediaProcedia Engineering 00 (2012) 000–000 Engineering 32 (2012) 827 – 832 www.elsevier.com/locate/procedia
I-SEEC2011
Luminescence of Nd3+- Doped Bi2O3-B2O3 Glass System K. Boonina,d∗ J. Kaewkhaob,d, N. Nuntawongc, P. Limsuwana,d a
Department of Physics, Faculty of Science,King Mongkut’s University of Technology Thonburi, Bangkok, Thailand, 10140 b Center of Excellence in Glass Technology and Materials Science, Nakhon Pathom Rajabhat University, Nakorn Pathom, Thailand 73000 c Photonic Technology Laboratory, National Electronics and Computer Technology Center, Pathumthani 12120, Thailand d Thailand Center of Excellence in Physics, CHE, Ministry of Education, Bangkok 10400, Thailand Elsevier use only: Received 30 September 2011; Revised 10 November 2011; Accepted 25 November 2011.
Abstract Absorption and luminescence properties of Nd3+ in B2O3-Bi2O3 glass system with composition xNd2O3:(70x)B2O3:30Bi2O3 are measured for the composition range 0≤x≤2.5 (in mol%). The glasses were prepared by normal melt-quench technique and investigated their optical and photoluminescence properties. From uv-visble spectrophotometer data, the various spectroscopic transitions observed are as follows: 4F3/2 (877 nm), 4F5/2 + 2H9/2 (803 nm), 4S3/2 + 4F7/2 (745 nm), 4F9/2 (684 nm), 2H11/2, (630 nm) 4G5/2 + 2G7/2(583 nm), 2K13/2 + 4G7/2 (526nm) 4G9/2 (519 nm) ← 4I9/2. The emission band at 900 1064 and 1336 nm arising from the transition 4F3/2→4I9/2, 4F3/2→4I11/2 and 4F3/2→4I13/2 respectively were observed when the sample was excited by lasers working at 750 nm. All intensity are increases with increasing of Nd2O3 concentration.
© 2010 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of I-SEEC2011 Keywords: Bismuth borate glass; Optical transmission spectra; Luminescence
1. Introduction Rare-earth doped bismuth borate glasses represent a group of materials that provide new opportunities for applications in ber-amplier and mid-infrared laser devices [1]. Compared with other glass hosts, bismuth borate glasses have some unique properties, as they typically possess a high refractive index. As a result, a large stimulated emission cross section and a low nonradiative relaxation rate [2] can be expected, which enhances the probabilities of observing new uorescent emission that is normally quenched in oxide glasses. This makes bismuth borate glasses extremely attractive as host materials for rare-earth ions [3]. In addition, because of their good chemical durabilities and good glass-forming * Corresponding author. E-mail address: [email protected].
1877-7058 © 2012 Published by Elsevier Ltd. doi:10.1016/j.proeng.2012.02.019
828 2
K. Boonin / Procedia Engineering 32 (2012) 827 – 832 K. Boonin et al.et/ al. Procedia Engineering 00 (2012) 000–000
abilities,bismuth borate glasses that have been doped with rare-earth ions show promise as ber amplier and ber oscillator materials. Nd3+ was the rst ion considered for ber-amplier and mid-infrared laser devices because it has a well-known four-level 4F3/2→4I9/2, 4F3/2→4I11/2, 4F3/2→4I13/2 and 4F3/2→4I15/2 transition. In this paper, the Nd3+ doped bismuth borate glasses with composition of 30Bi2O3:(100x)B2O3:xNd2O3 were investigated. The optical and photo luminescence properties change in bismuth borate glasses which containing difference Nd2O3 concentration. Nomenclature UV
Ultraviolet
VIS
Visible
NIR
Near Infrared luminescence
FWHM Full width at half maximum 2. Experimental The glass samples were prepared by using high purity Bi2O3, H3BO3 and Nd2O3 in the composition range of 30Bi2O3:(100-x)B2O3 :xNd2O3 where x = 0.0, 0.5, 1.0, 1.5, 2.0 and 2.5 mol%. Each batch weight about 20 g was melt in high alumina crucible by placing them in an electrical furnace for an hour, at 1,100 °C till a bubble free liquid was formed. These melts were quenched at room temperature in air by pouring between the melt on a stainless steel plate and pressing with another stainless steel plate. The quenched glasses were annealed at 450°C for 3 hour for reduce thermal stress [4], and cool down to the room temperature. All glass samples were cut and polish in proper shape for further studies. The absorption spectra were measured by UV-VIS-NIR spectrophotometer (Shimadzu UV-3100, JAPAN) with a spectral range from 200 to 2000 nm. Near infrared emission spectra were measured with a Quanta Master 3 luminescence spectrometer from Photon Technology International (PTI), using 750 nm excited radiation from a Xenon compact arc lamps. All the measurements were carried out at room temperature. 3. Results and discussions Absorption spectra of Nd3+ doped in bismuth borate glasses are shown in Fig. 1. The optical absorption edges are not sharply defined in glass samples under study, in accordance with their amorphous nature [5]. It can be seen that the transition energy levels vary with the Nd2O3 concentration and depend on covalency and the asymmetry of Nd-O local structure among these host matrices [6]. It is observed that the absorption intensity of the observed bands increase with the increase of Nd2O3 concentration. The absorption bands of Nd3+ correspond to transitions from the 4I9/2 ground state to various excited levels. These transitions were assigned by comparing the band positions in the absorption spectra with a standard wavelength chart for the Nd3+ ion [7]. The various spectroscopic transitions observed are as follows: 4F3/2 (877 nm), 4F5/2 + 2H9/2 (803 nm), 4S3/2 + 4F7/2 (745 nm), 4F9/2 (684 nm), 2 H11/2, (630 nm) 4G5/2 + 2G7/2(583 nm), 2K13/2 + 4G7/2 (526nm) 4G9/2 (519 nm) ← 4I9/2. Moreover, the absorption bands corresponding to 2D3/2, 2G9/2, 4G11/2, 2P1/2 ← 4I9/2 transitions were not clearly observed for the bismuth borate glass.
K.K. Boonin et et al.al. / Procedia Engineering 3200 (2012) 827 – 832 Boonin / Procedia Engineering (2012) 000–000
Fig. 1. Optical absorption spectra of Bi2O3-B2O3-Nd2O3 glass system
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K. Boonin / Procedia Engineering 32 (2012) 827 – 832 K. Boonin et al.et/ al. Procedia Engineering 00 (2012) 000–000
Fig. 2. 900 nm emission spectra of Nd3+ ions in bismuth borate glass samples of different compositions (Bi2O3 content indicated at the right side of the spectra). Pump wavelength was 750 nm
Fig. 3. 1.064 μm emission spectra of Nd3+ ions in bismuth borate glass samples of different compositions (Bi2O3 content indicated at the right side of the spectra). Pump wavelength was 750 nm
K.K.Boonin – 832 Booninetetal.al./ Procedia / ProcediaEngineering Engineering3200(2012) (2012)827 000–000
Fig. 4. 1.336 μm emission spectra of Nd3+ ions in bismuth borate glass samples of different compositions (Bi2O3 content indicated at the right side of the spectra). Pump wavelength was 750 nm
Of the many rare-earth ions, Nd3+ is well known for its favorable characteristics for laser transition[2]. the levels denoted 4F5/2 can be used to absorb light from a pumping source at about 800 nm. Ions excited into the pump band decay, usually nonradiatively, to the upper laser level 4F5/2 in a time that is short in comparison with its radiative lifetime (typically 300 - 600 s)[2]. From this upper laser level 4F3/2 there are four laser transitions 4I15/2 (1.80 μm), 4I13/2 (1.35 μm), 4I11/2 (1.06 μm), and 4I9/2 (0.88 μm). Fig. 2, 3 and 4 exhibit the NIR emission spectrum of samples when pumped by laser at 750 nm. Strong emission band with the center wavelength 0.9, 1.064 and 1.336 μm arising from the transition 4 F3/2→4I9/2, 4F3/2→4I11/2 and 4F3/2→4I13/2 respectively and the full width at half maximum (FWHM) were estimated to be about 52, 44 and 46 nm respectively. The composition dependence of the emission spectra as shown in Fig. 2, 3 and 4. Low Nd2O3 content favors comparably narrower spectra, increasing Nd2O3 content leads to broad. 3. Conclusions In this research, glasses from the system 30Bi2O3:(70-x)B2O3:xNd2O3 (x= 0.0, 0.5, 1.0, 1.5, 2.0, 2.5 mol%) were prepared by melt quenching technique. The absorption peaks at 4F3/2 (877 nm), 4F5/2 + 2H9/2 (803 nm), 4S3/2 + 4F7/2 (745 nm), 4F9/2 (684 nm), 2H11/2, (630 nm) 4G5/2 + 2G7/2(583 nm), 2K13/2 + 4G7/2 (526nm) 4G9/2 (519 nm) of Nd2O3 in bismuth borate glasses were observed. The emission band at 0.9, 1.064 and 1.336 µm arising from the transition 4F3/2→4I9/2, 4F3/2→4I11/2 and 4F3/2→4I13/2 respectively were observed when the sample was excited by lasers working at 750 nm. All intensity are increases with increasing of Er2O3 concentration. The red shift, found for increasing Er2O3 content in the peak wave length of the band.
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K. Boonin / Procedia Engineering 32 (2012) 827 – 832 K. Boonin et al.et/ al. Procedia Engineering 00 (2012) 000–000
Acknowledgements The authors wish to thank National Research Council of Thailand (NRCT) funding this research. Thanks are also due to Research and Development Institute, NPRU for facilities. P. Limsuwan wish to thank commission of Higher Education (NRU Project) for financial support. 6. References [1] Little G. Lakshminarayana, R . Vidya Sagar, S. Buddhudu. NIR luminescence from Er3+/Yb3+,Tm3+/Yb3+,Er3+/Tm3+ and Nd3+ ions-doped zincborotellurite glasses for optical amplication. J. Luminescence 2008; 128: 690-695. [2] M. Yamane, Y. Asahara, Glass for photonic. London, England: THE PRESS SYNDICATE OF THE UNIVERSITY OF CAMBRIDGE; 2004. [3] Y. Q. Qiu, J. Kang, C. X. Li, X. Y. Dong, C.L. Zhao. Broadband NearInfrared Luminescence in Bismuth Borate Glasses. Laser Physics 2010; 20: 487–492. [4] A. Thulasiramudu, S. Budduhudu. . J. Quant. Spec. Radiat. Trans 2006. 97: p.181 [5] B. Eraiah, Sudha G. Bhat. Optical properties of samarium doped zinc–phosphate glasses. J. of Phy. Chem. of Sol 2007. 68: 581-585. [6] B. Karthikeyana, S. Mohanb, M.L. Baesso. . Physica B 2003. 337: 249. [7] G.H. Dieke. Spectra and Energy Levels of Rare-Earth Ions in Crystals. New York: John Wiley & sons; 1969.