Au/Bi共掺二氧化硅薄膜的制备及近红外光谱调控
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摘要
根据X射线光电子能谱分析和选择性光致发光谱测试结果,探讨了Bi离子掺杂非晶二氧化硅薄膜的近红外发光来源。我们认为非晶二氧化硅薄膜中Bi离子的近红外发光来源于低价态Bi~+离子从轨道~3P_1层到~3P_0层的辐射复合跃迁和Bi~0从轨道~2D_(3/2)层到~4S_(3/2)层的辐射复合跃迁。此外,本文利用限制性晶化原理,通过在掺Bi二氧化硅薄膜中引入Au离子,实现了Bi离子相关的近红外发光峰位可调,荧光强度增大了300%。高分辨透射电子显微镜截面图片证实了非晶二氧化硅薄膜厚度约为90 nm以及不同尺寸、数密度Au量子点的形成。变温光致发光谱测试结果表明,部分Au离子可有效降低Bi离子掺杂非晶二氧化硅薄膜中羟基集团等非辐射复合中心密度。Bi离子掺杂非晶二氧化硅薄膜近红外发光来源的探讨以及通过Au量子点调控Bi离子近红外发光性质的讨论将有助于未来掺Bi发光材料的相关研究。
Near-infrared luminescence origin of Bi-doped amorphous silica thin film is discussed by the XPS characterizations and selective PL measurements. The nature of the near-infrared emission in amorphous silica thin film is considered as both the transition of Bi~+ ions from ~3P_1 to ~3P_0 and the transition of Bi~0 from ~2D_(3/2) to ~4S_(3/2). Further, the confined crystallization growth strategy is designed for fabricating uniform-size Au quantum dots embedded in Bi-doped silica thin film. Through controls of the doping amounts of Au ions, the NIR emission of Bi ions in silica thin film can be wavelength-tunable and enhanced by nearly 300% on the optimum Au ions doping amount. The thickness of thin film is 90 nm and the formation of Au quantum dots with different average sizes and number densities have been confirmed by the high-resolution TEM images. Temperature-dependent PL emission spectra suggest parts of Au ions may play a role of eliminating hydroxyl groups, which gives rises to greatly enhanced PL intensity in the near-infrared region. We anticipate that both greatly enhanced and wavelength-tunable NIR luminescence and discussion of luminescence origin would shed light on future research of Bi ions-doped luminescent materials.
Near-infrared luminescence origin of Bi-doped amorphous silica thin film is discussed by the XPS characterizations and selective PL measurements. The nature of the near-infrared emission in amorphous silica thin film is considered as both the transition of Bi~+ ions from ~3P_1 to ~3P_0 and the transition of Bi~0 from ~2D_(3/2) to ~4S_(3/2). Further, the confined crystallization growth strategy is designed for fabricating uniform-size Au quantum dots embedded in Bi-doped silica thin film. Through controls of the doping amounts of Au ions, the NIR emission of Bi ions in silica thin film can be wavelength-tunable and enhanced by nearly 300% on the optimum Au ions doping amount. The thickness of thin film is 90 nm and the formation of Au quantum dots with different average sizes and number densities have been confirmed by the high-resolution TEM images. Temperature-dependent PL emission spectra suggest parts of Au ions may play a role of eliminating hydroxyl groups, which gives rises to greatly enhanced PL intensity in the near-infrared region. We anticipate that both greatly enhanced and wavelength-tunable NIR luminescence and discussion of luminescence origin would shed light on future research of Bi ions-doped luminescent materials.
引文
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[2] ZHOU Y,YONG Z J,ZHANG W,et al..Ultra-broadband optical amplification at telecommunication wavelengths achieved by bismuth-activated lead iodide perovskites [J].J.Mater.Chem.C,2017,5(10):2591-2596.
[3] FIRSTOV S,KHARAKHORDIN A,ALYSHEV S,et al..Formation of laser-active centers in bismuth-doped high-germania silica fibers by thermal treatment [J].Opt.Express,2018,26(10):12363-12371.
[4] ESCUDERO A,CARRILLO-CARRIóN C,ZYUZIN M V,et al..Synthesis and functionalization of monodisperse near-ultraviolet and visible excitable multifunctional Eu3+,Bi3+∶REVO4 nanophosphors for bioimaging and biosensing applications [J].Nanoscale,2016,8(24):12221-12236.
[5] 刘义章,孙军勇,王磊,等.半导体聚合物量子点-亚甲基蓝荧光能量转移体系测定水中Bi3+ [J].发光学报,2017,38(10):1353-1358.LIU Y Z,SUN J Y,WANG L,et al..Semiconducting polymer dots-methylene blue fluorescence energy transfer system for determination of Bi (Ⅲ) ions in water [J].Chin.J.Lumin.,2017,38(10):1353-1358.(in Chinese)
[6] SOKOLOV V O,PLOTNICHENKO V G,DIANOV E M.The origin of near-IR luminescence in bismuth-doped silica and germania glasses free of other dopants:first-principle study [J].Opt.Mater.Express,2013,3(8):1059-1074.
[7] DIANOV E M.Bismuth-doped optical fibers:a challenging active medium for near-IR lasers and optical amplifiers [J].Light:Sci.Appl.,2012,1:e12-1-7.
[8] LI X M,CAO J K,PENG M Y.The origin of the heterogeneous distribution of bismuth in aluminosilicate laser glasses [J].J.Am.Ceram.Soc.,2018,101(7):2921-2929.
[9] XIA H P,WANG X J.Near infrared broadband emission from Bi5+-doped Al2O3-GeO2-X(X=Na2O,BaO,Y2O3) glasses [J].Appl.Phys.Lett.,2006,89(5):051917-1-3.
[10] HE X J,XU X H,ZHOU D C,et al..Effects of copper ions on the near-infrared luminescence in Bi doped silicate glass via copper for sodium ion exchange [J].J.Non-Cryst.Solids,2015,421:30-34.
[11] PENG M Y,SPRENGER B,SCHMIDT M A,et al..Broadband NIR photoluminescence from Bi-doped Ba2P2O7 crystals:insights into the nature of NIR-emitting bismuth centers [J].Opt.Express,2010,18(12):12852-12863.
[12] LI X M,CAO J K,WANG L P,et al..Predictable tendency of Bi NIR emission in Bi-doped magnesium aluminosilicate laser glasses [J].J.Am.Ceram.Soc.,2018,101(3):1159-1168.
[13] ZHAO Q C,ZHANG J Z,LUO Y H,et al..Energy transfer enhanced near-infrared spectral performance in bismuth/erbium codoped aluminosilicate fibers for broadband application [J].Opt.Express,2018,26(14):17889-17898.
[14] CAO J K,LI X M,WANG L P,et al..New strategy to enhance the broadband near-infrared emission of bismuth-doped laser glasses [J].J.Am.Ceram.Soc.,2018,101(6):2297-2304.
[15] LIN S B,ZHANG X W,ZHANG P,et al..High-efficiency near-infrared emission from bismuth-doped SiO0.73 thin films fabricated by ion implantation technology [J].Opt.Lett.,2016,41(3):630-633.
[16] 董恒平,陈坤基,宗波,等.非晶掺氧氮化硅薄膜中N-Si-O发光缺陷态的研究 [J].南京大学学报(自然科学),2017,53(3):392-398.DONG H P,CHEN K J,ZONG B,et al..Investigation on luminescent defect state related to N-Si-O bonding in amorphous oxygenated silicon nitride film [J].J.Nanjing Univ.(Nat.Sci.),2017,53(3):392-398.(in Chinese)
[17] FUJIMOTO Y.Local structure of the infrared bismuth luminescent center in bismuth-doped silica glass [J].J.Am.Ceram.Soc.,2010,93(2):581-589.
[18] ZHANG X W,LIN T,ZHANG P,et al..Tunable quantum dot arrays as efficient sensitizers for enhanced near-infrared electroluminescence of erbium ions [J].Nanoscale,2018,10(8):4138-4146.
[19] ZHANG P X,CHEN N,WANG R,et al..Charge compensation effects of Yb3+ on the Bi+:near-infrared emission in PbF2 crystal [J].Opt.Lett.,2018,43(10):2372-2375.
[20] ZHANG N,QIU J R,DONG G P,et al..Broadband tunable near-infrared emission of Bi-doped composite germanosilicate glasses [J].J.Mater.Chem.,2012,22(7):3154-3159.
[21] WANG R F,LIU J,ZHANG Z.Luminescence and energy transfer progress in Bi-Yb co-doped germanate glass [J].J.Alloys Compd.,2016,688:332-336.
[22] JIA X M,XIA M L,XU Y S,et al..Silver nanoparticle enhanced 2.7 μm luminescence in Er3+-doped bismuth germanate glasses [J].Opt.Mater.Express,2018,8(6):1625-1632.
[23] ZHANG X W,CHEN R W,WANG P J,et al..A soft chemistry-based route to enhanced photoluminescence of terbium ions and tin oxide nanocrystals codoped silica thin films [J].Appl.Surf.Sci.,2018,452:96-101.
[24] 林涛,万能,韩敏,等.SnO2纳米晶体的制备、结构与发光性质 [J].物理学报,2009,58(8):5821-5825.LIN T,WAN N,HAN M,et al..Synthesis,structures and luminescence properties of SnO2 nanoparticles [J].Acta Phys.Sinica,2009,58(8):5821-5825.(in Chinese).
[25] ZHANG X W,LIN T,ZHANG P,et al..Highly efficient near-infrared emission in Er3+ doped silica films containing size-tunable SnO2 nanocrystals [J].Opt.Express,2014,22(1):369-376.