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掺Bi离子锗铌酸盐红外发光玻璃的研究

赵鹤玲 夏海平 罗彩香 徐军

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掺Bi离子锗铌酸盐红外发光玻璃的研究

赵鹤玲, 夏海平, 罗彩香, 徐军

Bi-doped germanium niobate glasses with near-infrared broad-band emission

Zhao He-Ling, Xia Hai-Ping, Luo Cai-Xiang, Xu Jun
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  • 用高温熔融法制备了Bi2O3掺杂的(0.9-x) GeO2-xNb2O5-0.1BaO (含量x为摩尔分数, x=0, 0.04, 0.07, 0.1)系列玻璃. 测定了玻璃样品的差热分析(DTA)曲线、吸收光谱、发射光谱及X射线光电子能谱(XPS). 从DTA曲线分析得到玻璃的结晶起始温度与软化温度之差(Tx-Tg)达200℃以上. 吸收光谱中可观察到位于500, 700, 808和1000 nm处的吸收峰, 并随着Nb2O5含量x的增加吸收边带发生红移. 在波长为808 nm激光激发下, 观察到发光中心位于1300 nm处、荧光光谱半高宽约为200 nm的宽带发光. 荧光强度随Bi2O3掺杂量的增加先增强后减弱, 当掺杂量达到约0.01时, 荧光强度达到最强. 随着Nb2O5含量x从0.04增加到0.1时, 荧光强度逐步减弱. 样品的XPS峰分别位于159.6和164.7 eV, 它们介于Bi3+与Bi5+的特征结合能之间, 因此Bi3+与Bi5+可能同时存在于玻璃基质中. 从XPS及Bi离子的发光特性推断, 宽带的荧光发射可能起因于Bi5+. 随着Nb2O5含量x的增加, 荧光强度逐步减弱. 分析认为, Nb2O5取代GeO2后形成了NbGe缺陷, 需要低价Bi离子进行电子补偿, 因而抑制了Bi5+形成, 致使荧光强度减弱.
    The Bi2O3 doped glasses with concentrations of (0.9-x) GeO2-xNb2O5-0.1BaO (x=0.04, 0.07, 0.1) glasses are prepared by the conventional melting method. The differential thermal analysis (DTA) curves, the absorption spectra, the fluorescence decay curve and the X-ray photoelectron spectra are measured. The difference between glass crystallization onset temperature and transition temperature (Tx-Tg) of the glasses is up to 200℃ from the DTA curve. Absorption peaks at 500, 700, and 1000 nm are observed. The absorption edges show a red-shift with the increase of Nb2O5 content x. The emission band at 1300 nm with the full width at half maximum near 200 nm is observed under the excitation of 808 nm laser. The fluorescence intensity increases with the increase of the concentration of Bi2O3. The fluorescence intensity reaches a maximal value when the concentration of Bi2O3 is about 0.01. The peaks of binding energy in XPS are located at 159.6 and 164.7 eV respectively. The binding energy peaks are located between those of Bi3+ and Bi5+ by comparing with those of Bi2O3 (Bi3+) and NaBiO3 (Bi5+). According to the XPS results, one may conclude that Bi3+ and Bi5+ ions co-exist in the glass. The near infrared broadband emission may be assigned to Bi5+ ion based on the results of emission spectra and X-ray photoelectron spectra. The broadband intensity is gradually weakened as the Nb2O5 content x increases from 0.04 to 0.1. As GeO2 is substituted by Nb2O5, complex NbGe defects are formed and the lower valence state of Bi ions will be inevitably formed to compensate the extra electric charge from Nb5+, thus resulting in the inhibition of Bi5+ and weakening the fluorescence aforementioned.
    • 基金项目: 国家自然科学基金(批准号: 50972061)、浙江省自然科学基金(批准号: R4100364)、宁波市自然科学基金(批准号: 2009A610007)和宁波大学王宽诚幸福基金资助的课题.
    • Funds: Project supported by the National Natural Science Foundation of China (Grant No. 50972061), the Natural Science Foundation of Zhejiang Province, China (Grant No. R4100364), the Natural Science Foundation of Ningbo, China (Grant No. 2009A610007), and the K. C. Wong Magna Foundation of Ningbo University, China.
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    Zhou S F 2007 Appl. Phys. Lett. 91 061919

    [2]

    Qiu J R, Peng M Y, Ren J J, Meng X G, Jiang X W, Zhu C S 2008 J. Non-Cryst. Solids 354 1235

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    Chi G W, Zhou D C, Song Z G, Qiu J B 2009 Opt. Mater. 31 945

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    [5]

    Blasse G, Brill A 1997 J. Chem. Phys. 47 1920

    [6]

    Srivastava M A 1998 J. Lumin. 78 239

    [7]

    Blasse G, Brill A 1968 J. Chem. Phys. 48 217

    [8]

    Dong W, Zhu C 2003 J. Phys. Chem. Solids 64 265

    [9]

    Murata T, Mour T 2007 J. Non-Cryst. Solids 353 2403

    [10]

    Fujimoto Y, Nakatsuka M 2001 Jpn. J. Appl. Phys. 40 L279

    [11]

    Yu C, Xia H P, Luo C X, Hu Y, Chen H B, Xu J 2010 Chin. J. Lasers 37 2610 (in Chinese) [虞灿, 夏海平, 罗彩香, 胡元, 陈红兵, 徐军 2010 中国激光 37 2610]

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    Fujimoto Y, Nakatsuka M 2003 Appl. Phys. Lett. 82 3325

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    Wang X J, Xia H P 2006 Acta Phys. Sin. 55 5263 (in Chinese) [王雪俊, 夏海平 2006 物理学报 55 5263]

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    Xu J, Ma X S, Gu J, Sheng Y F, Zhang X M 1990 J. Synth. Cryst. 19 283 (in Chinese) [徐军, 马笑山, 顾及, 沈雅芳, 张新民 1990 人工晶体学报 19 283]

    [15]

    Duffy J A 1996 J. Non-Cryst. Solids 196 45

    [16]

    Fujimoto Y 2010 J. Am. Ceram. Soc. 93 581

    [17]

    Wang Y L, Dai S X, Xu T F, Nie Q H, Sheng X, Wang X S 2008 Acta Photon. Sin. 37 89 (in Chinese) [王艳玲, 戴世勋, 徐铁峰, 聂秋华, 沈祥, 王训四 2008 光子学报 37 89]

    [18]

    Peng M Y, Qiu J R, Chen D, Meng X G, Yang I, Jiang X W, Zhu C 2004 Opt. Lett. 29 1998

    [19]

    Xu T F, Zhang X D, Nie Q H, Dai S X, Seng X, Liang X W, Zhang X H 2006 J. Rare Metals 30 6 (in Chinese) [徐铁峰, 张旭东, 聂秋华, 戴世勋, 沈祥, 梁晓炜, 章向华 2006 稀有金属 30 6]

    [20]

    Jiang X, Animesh J 2010 Opt. Mater. 33 14

    [21]

    Yang J H, Dai S X, Wen L, Liu Z P, Hu L L, Jiang Z H 2003 Acta Phys. Sin. 52 508 (in Chinese) [杨建虎, 戴世勋, 温磊, 柳祝平, 胡丽丽, 姜中宏 2003 物理学报 52 508]

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    Wagner C D 1990 Auger and X-Ray Photoelectron Spectroscopy (2nd ed) (New York: John Wiley) Vol 1

    [23]

    Blasse G, Meijierink A, Nomes M, Zuidema J 1994 J. Phys. Chem. Solids 55 171

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出版历程
  • 收稿日期:  2011-03-22
  • 修回日期:  2012-04-28
  • 刊出日期:  2012-04-20

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