Zn~(2+)掺杂诱导Eu~(3+)激活BiOCl层状半导体的反常发光性能研究
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摘要
采用固相法在500℃下成功制备Zn~(2+)掺杂BiOCl:Eu~(3+)层状半导体,并研究了Zn~(2+)(0~20mol%)掺杂对Eu~(3+)激活BiOCl层状半导体发光性能的影响。利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)、傅里叶变换红外光谱(FT-IR)、激发–发射光谱、荧光寿命衰减曲线对样品的结构和性能进行表征。研究发现,随Zn~(2+)掺杂浓度增大,BiOCl晶体结构不变,Eu~(3+)荧光寿命延长,但发光强度却出现先减后增的反常现象。综合分析表明这可能与BiOCl特殊的层状结构有关。通过XRD和XPS的表征可以推断:当Zn~(2+)掺杂浓度≤10mol%,Zn~(2+)在BiOCl中掺杂方式以晶胞层间隙掺杂为主;当Zn~(2+)掺杂浓度>10mol%后,掺杂方式逐渐向取代掺杂转变。两种掺杂机制对Eu~(3+)荧光寿命的改变以及形成缺陷对基质能量传递效率的影响可能是形成上述反常现象的主要原因。研究结果有助于认识稀土掺杂层状半导体的发光性能及影响规律,并对Eu~(3+)掺杂BiOCl这类新型发光材料的开发设计具有指导意义。
Eu~(3+)-activated BiOCl layered phosphors induced by doping Zn~(2+) were prepared by traditional solid reaction method, and the effect of Zn~(2+) ion dopants(0-20mol%) on the photoluminescence properties were characterized by X-ray powder diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM), Fourier transform infrared absorption(FT-IR), excitation and emission spectra, and luminescence decay curves measurement. It is found that increase of concentration of Zn~(2+) ion dopants almost has no influence on the structure of BiOCl crystals but decreases the emission intensity of Eu~(3+) ion at first and then increases it, accompanying with continually enhancing luminescence lifetime of Eu~(3+) ions. The comparative experiments suggest that this results are involved in special layered structure of BiOCl semiconductor. Zn~(2+) ions would be incorporated into interlayer space of the BiOCl layered crystals when the concentration of Zn~(2+) ions ≤10%. Then, Zn~(2+) ions tend to incorporate into crystal lattices by substituting Bi3+ ions. Different doping mechanism of Zn~(2+) may change Eu~(3+) lifetime and modify energy transfer efficiency from the host, leading to above emission behavior of Eu~(3+) ion dopants. The result is helpful to improve performance of novel red Eu~(3+) doped BiOCl phosphor and to understand emission property of rare earth ion in layered phosphors.
Eu~(3+)-activated BiOCl layered phosphors induced by doping Zn~(2+) were prepared by traditional solid reaction method, and the effect of Zn~(2+) ion dopants(0-20mol%) on the photoluminescence properties were characterized by X-ray powder diffraction(XRD), X-ray photoelectron spectroscopy(XPS), scanning electron microscopy(SEM), Fourier transform infrared absorption(FT-IR), excitation and emission spectra, and luminescence decay curves measurement. It is found that increase of concentration of Zn~(2+) ion dopants almost has no influence on the structure of BiOCl crystals but decreases the emission intensity of Eu~(3+) ion at first and then increases it, accompanying with continually enhancing luminescence lifetime of Eu~(3+) ions. The comparative experiments suggest that this results are involved in special layered structure of BiOCl semiconductor. Zn~(2+) ions would be incorporated into interlayer space of the BiOCl layered crystals when the concentration of Zn~(2+) ions ≤10%. Then, Zn~(2+) ions tend to incorporate into crystal lattices by substituting Bi3+ ions. Different doping mechanism of Zn~(2+) may change Eu~(3+) lifetime and modify energy transfer efficiency from the host, leading to above emission behavior of Eu~(3+) ion dopants. The result is helpful to improve performance of novel red Eu~(3+) doped BiOCl phosphor and to understand emission property of rare earth ion in layered phosphors.
引文
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[2]LI Y J,ZHAO Z Y,SONG Z G,et al.Far-red-emitting Bi OCl:Eu3+phosphor with excellent broadband NUV-excitation for white-lightemitting diodes.J.Am.Ceram.Soc.,2015,98(7):2170–2176.
[3]XIAO L H,GU M,LIU X L,et al.Effects of Zn2+doping on the structural and luminescent properties of Gd Ta O4:Eu3+phosphors.Spectroscopy and Spectral Analysis,2007,27(6):1054–1057.
[4]LI J,YU Y,ZHANG L Z.Bismuth oxyhalide nanomaterials:layered structures meet photocatalysis.Nanoscale,2014,6(15):8473–8488.
[5]LI G Q,ZHANG X C,DING G Y,et al.Study on the atomic and electronic structures of Bi OCl{001}surface using first principles.Acta Phys.Sin.,2013,62(12):127301.
[6]OZAWA T C,FUKUDA K,AKATSUKA K,et al.(K1.5Eu0.5)Ta3O10:a far-red luminescent nanosheet phosphor with the double perovskite structure.J.Phys.Chem.C,2008,112(44):17115–17120.
[7]LI Y J,SONG Z G,LI C,et al.High multi-photon visible upconversion emissions of Er3+singly doped Bi OCl microcrystals:a photon avalanche of Er3+induced by 980 nm excitation.Appl.Phys.Lett.,2013,103(23):231104.
[8]KUANG Q L,LI Y J,QIU J B,et al.Synthesis and luminescence properties of Bi OCl:Dy3+phosphors for NUV excited white light-emitting diodes.Spectroscopy and Spectral Analysis,2015,35(4):889–893.
[9]LI Y J,SONG Z G,WAN R H,et al.Multi-band photon avalanche controlling performance of Bi OCl:Er3+crystals through facile Yb3+doping.J.Mater.Chem.C,2015,3(33):8559–8565.
[10]LI Y J,HUANG Y B,LIU Q,et al.Color-tunableness of Er3+/Eu3+co-doped Bi OCl phosphors for near ultraviolet excitation.Acta Phys.Sin.,2015,64(17):0177803.
[11]SINGH B P,RAMAKRISHNA P V,SINGH S,et al.Improved photo-luminescence behaviour of Eu3+activated Ca Mo O4 nanoparticles via Zn2+incorporation.RSC Adv.,2015,5(69):55977–55985.
[12]JU Q,LIU Y S,LI R F,et al.Optical spectroscopy of Eu3+-doped Ba FCl nanocrystals.J.Phys.Chem.C,2009,113(6):2309–2315.
[13]FERREIRA R S,NOBRE S S,GRANADEIRO C M,et al.A theoretical interpretation of the abnormal 5D0→7F4 intensity based on the Eu3+local coordination in the Na9[Eu W10O36]·14H2O polyoxometalate.J.Lumin.,2006,121(2):561–567.
[14]SARAF R,SHIVAKUMARA C,BEHERA S,et al.Photoluminescence,photocatalysis and Judd-Ofelt analysis of Eu3+-activated layered Bi OCl phosphors.RSC Adv.,2015,5(6):4109–4120.
[15]MURPHY D W,CHRISTIAN P A,DISALVOF F J,et al.Lithium incorporation by vanadium pentoxide.Inorg.Chem.,1979,18(10):2800–2803.
[16]LI W T,HUANG W Z,ZHOU H,et al.Synthesis of Zn2+doped Bi OCl hierarchical nanostructures and their exceptional visible light photocatalytic properties.J.Alloys Compd.,2015,638:148–154.
[17]ZHANG X B,ZHANG L,HU J S,et al.Facile hydrothermal synthesis and improved photocatalytic activities of Zn2+doped Bi2Mo O6 nanosheets.RSC Adv.,2016,6(38):32349–32357.
[18]SONG J M,MAO C J,NIU H L,et al.Hierarchical structured bismuth oxychlorides:self-assembly from nanoplates to nanoflowers via a solvothermal route and their photocatalytic properties.Cryst Eng Comm,2010,12(11):3875–3881.
[19]MI Y,ZHOU M,WEN L Y,et al.A highly efficient visible-light driven photocatalyst:two dimensional square-like bismuth oxyiodine nanosheets.Dalton Trans.,2014,43(25):9549–9556.
[20]DAI Q L,SONG H W,WANG M Y,et al.Size and concentration effects on the photoluminescence of La2O2S:Eu3+nanocrystals.J.Phys.Chem.C,2008,112(49):19399–19404
[21]MAHATA M K,KOPPE T,MONDAL T,et al.Incorporation of Zn2+ions into Ba Ti O3:Er3+/Yb3+nanophosphor:an effective way to enhance upconversion,defect luminescence and temperature sensing.Phys.Chem.Chem.Phys.,2015,17(32):20741–20753.
[22]PARK J C,MOON H K,KIM D K,et al.Morphology and cathodoluminescence of Li-doped Gd2O3:Eu3+,a red phosphor operating at low voltages.Appl.Phys.Lett.,2000,77(14):2162.