Zn_2GeO_4∶Mn~(2+)绿色磷光粉的制备和长余辉性能
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摘要
采用高温固相反应法合成了Zn_2GeO_4∶xMn~(2+)系列绿色长余辉磷光粉。XRD分析结果表明,掺锰磷光粉的主要衍射峰位与锗酸锌晶体标准卡基本一致,但略有红移。SEM照片显示,相对于Zn_2GeO_4基质平均粒径而言,掺锰磷光粉的颗粒尺寸均增大。在325 nm紫外光激发下,Zn_2GeO_4∶Mn~(2+)发射出强的530 nm绿光,优化掺锰离子浓度为0.5%。同时发现Zn_2GeO_4∶0.2Mn~(2+)磷光粉暗场条件下的余辉时间超过180 min,详细讨论了Zn_2GeO_4∶Mn~(2+)长余辉发光的内在机理。
A series of Zn_2GeO_4∶xMn~(2+)green long afterglow phosphors have been synthesized by high temperature solid-state reaction method. XRD results show that the main diffraction peaks of phosphors doped Mn~(2+)ions are basically consistent with those in standard card of Zn_2GeO_4 crystal,but there exists slightly red shift. SEM photos present the particle sizes of phosphors doped different Mn~(2+)ions are all enlarged compared to average grain size of Zn_2GeO_4 host. The intense 530 nm green emissions from Zn_2GeO_4∶ Mn~(2+)phosphors can be gained under 325 nm ultraviolet excitation and optimal Mn~(2+)doping concentration is 0. 5%. At the same time,it is found that the afterglow time of Zn_2GeO_4∶0. 2Mn~(2+)phosphor exceeds 180 min under the condition of dark environment,and the internal mechanism of long afterglow luminescence of Zn_2GeO_4∶Mn~(2+)phosphor is discussed in detail.
A series of Zn_2GeO_4∶xMn~(2+)green long afterglow phosphors have been synthesized by high temperature solid-state reaction method. XRD results show that the main diffraction peaks of phosphors doped Mn~(2+)ions are basically consistent with those in standard card of Zn_2GeO_4 crystal,but there exists slightly red shift. SEM photos present the particle sizes of phosphors doped different Mn~(2+)ions are all enlarged compared to average grain size of Zn_2GeO_4 host. The intense 530 nm green emissions from Zn_2GeO_4∶ Mn~(2+)phosphors can be gained under 325 nm ultraviolet excitation and optimal Mn~(2+)doping concentration is 0. 5%. At the same time,it is found that the afterglow time of Zn_2GeO_4∶0. 2Mn~(2+)phosphor exceeds 180 min under the condition of dark environment,and the internal mechanism of long afterglow luminescence of Zn_2GeO_4∶Mn~(2+)phosphor is discussed in detail.
引文
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[18]MLLER M,VOLHARD M F,JSTEL T.Photoluminescence and afterglow of deep red emitting Sr Sc2O4∶Eu2+[J].RSCAdv.,2016,6(10):8483-8488.
[19]MERONI D,PORATI L,DEMARTIN F,et al..Sol-gel synthesis of Ca Ti O3∶Pr3+red phosphors:tailoring the synthetic parameters for luminescent and afterglow applications[J].ACS Omega,2017,2(8):4972-4981.
[20]ZHUANG Y X,UEDA J,TANABE S.Photochromism and white long-lasting persistent luminescence in Bi3+-doped ZnGa2O4ceramics[J].Opt.Mater.Express,2012,2(10):1378-1383.
[21]JIN Y,BAI Y M,GE M Q.Preparation and luminescence properties of a white emitting long afterglow luminous fiber based on FRET[J].J.Rare Earths,2016,34(4):374-380.
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[23]张秋函,谭慧英,刘永冲,等.纳米纤维状Sr3Al2O5Cl2∶Eu2+,Tm3+的白色长余辉性能[J].发光学报,2017,38(6):697-701.ZHANG Q H,TAN H Y,LIU Y C,et al..White long persistent phenomenon from Sr3Al2O5Cl2∶Eu2+,Tm3+nano-fiber[J].Chin.J.Lumin.,2017,38(6):697-701.(in Chinese)
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[27]SINGH S K.Red and near infrared persistent luminescence nano-probes for bioimaging and targeting applications[J].RSC Adv.,2014,4(102):58674-58698.
[28]BAKLANOVA Y V,ENYASHIN A N,MAKSIMOVA L G,et al..Sensitized IR luminescence in Ca3Y2Ge3O12∶Nd3+,Ho3+under 808 nm laser excitation[J].Ceram.Int.,2018,44(6):6959-6967.
[29]TAKEMOTO M,ISEKI T.Fluorescence and afterglow of Ca2Sn2Al2O9∶Mn2+[J].J.Phys.Chem.Solids,2018,114:88-93.
[30]过诚,丛妍,董斌,等.(Zn1-x,Mgx)2Ge O4∶Mn2+的荧光以及长余辉发光性能[J].发光学报,2017,38(9):161-1166.GUO C,CONG Y,DONG B,et al..Photoluminescence and long-lasting phosphorescence characteristics of(Zn1-x,Mgx)2Ge O4∶Mn2+[J].Chin.J.Lumin.,2017,38(9):1161-1166.(in Chinese)
[31]MJAKIN S V,MINAKOVA T S,BAKHMETYEV V V,et al..Effect of the surfaces of Zn3(PO4)2∶Mn2+phosphors on their luminescent properties[J].Russ.J.Phys.Chem.A,2016,90(1):240-245.
[32]SUN X Y,HE Z,GU X.Tunable luminescence for KNa Ca2(PO4)2∶Eu2+/Mn2+phosphors due to energy transfer from Eu2+to Mn2+[J].J.Mater.Sci.Mater.Electron.,2018,29(8):6961-6965.
[2]ZHANG D D,LIU J M,SONG N,et al..Fabrication of mesoporous La3Ga5Ge O14∶Cr3+,Zn2+persistent luminescence nanocarriers with super-long afterglow for bioimaging-guided in vivo drug delivery to the gut[J].J.Mater.Chem.B,2018,6(10):1479-1488.
[3]TROJAN-PIEGZA J,ZYCH E.Afterglow luminescence of Lu2O3∶Eu ceramics synthesized at different atmospheres[J].J.Phys.Chem.C,2014,114(9):4215-4220.
[4]EBRAHIMZADE A,MOJTAHEDI M R M,RAHBAR R S.Study on characteristics and afterglow properties of luminous polypropylene/rare earth strontium aluminate fiber[J].J.Mater.Sci.Mater.Electron.,2017,8(11):8167-8176.
[5]SATO K,KOMURO S,MORIKAWA T,et al..Long afterglow characteristics of thin film phosphor fabricated by laser ablation[J].J.Cryst.Growth,2005,275(1-2):e1137-e1141.
[6]史晨,龙啸云,侯雪斌,等.具有光致变色功能的长余辉发光再生纤维素纤维的光学性能[J].高分子材料科学与工程,2017,33(6):95-99.SHI C,LONG X Y,HOU X B,et al..Optical performaces of photochromic and long afterglow luminescent regenerated cellulose fiber[J].Polym.Mater.Sci.Eng.,2017,33(6):95-99.(in Chinese)
[7]TAKAHASHI A,UMEGAKI T,KOJIMA Y.Effect of RE3+codopant on afterglow time of Sr S∶Eu2+,RE3+[J].Key Eng.Mater.,2014,617:131-134.
[8]郭崇峰,初本莉,徐剑,等.氧化物膜包覆碱土硫化物荧光粉的研究[J].发光学报,2004,25(4):449-454.GUO C F,CHU B L,XU J,et al..Improving the stability of alkaline earth sulfide based phosphors by oxide coating[J].Chin.J.Lumin.,2004,25(4):449-454.(in Chinese)
[9]HUANG Y M,MA Q L.Long afterglow of trivalent dysprosium doped strontium aluminate[J].J.Lumin.,2015,160:271-275.
[10]HU X W,YANG H,GUO T T,et al..Preparation and properties of Eu and Dy co-doped strontium aluminate long afterglow nanomaterials[J].Ceram.Int.,2018,44(7):7535-7544.
[11]XUE F H,HU Y H,FAN L M,et al..Photoluminescence and afterglow of Mn2+doped lithium zinc silicate[J].J.Lumin.,2016,183:68-72.
[12]肖玲,周建,刘桂珍.Li+掺杂Sr2Mg Si2O7∶Eu2+,Dy3+长余辉材料的发光性能[J].发光学报,2017,38(9):1143-1148.XIAO L,ZHOU J,LIU G Z.Luminescent properties of Li+doped Sr2Mg Si2O7∶Eu2+,Dy3+phosphors[J].Chin.J.Lumin.,2017,38(9):1143-1148.(in Chinese)
[13]CLYNE M A A,HALSTEAD C J,THRUSH B A.The kinetics of elementary reactions involving the oxides of sulphur.I.The nature of the sulphur dioxide afterglow[J].Proc.Roy.Soc.London Ser.A Math.Phy.Sci.,1966,295(1443):355-362.
[14]李进,袁良杰,孙聚堂,等.掺杂Eu2+的新型锶铝复合硫氧化物红色发光材料[J].中国稀土学报,2002,20(6):597-600.LI J,YUAN L J,SUN J T,et al..New red-emitting Eu2+-doped strontium-aluminium composite oxysulfide phosphorescent materials[J].J.Chin.Rare Earth Soc.,2002,20(6):597-600.(in Chinese)
[15]CHEN R,HU Y H,CHEN L,et al..Observation on a novel green-yellow afterglow in Tb3+-doped Sr3Al2O5Cl2phosphor[J].Sci.Adv.Mater.,2017,9(3-4):392-397.
[16]XU X H,WANG Y H,GONG Y,et al..Ca Al2O4∶Eu2+,Nd3+,Sr2+:a white-light phosphor with yellow-green long afterglow[J].Electrochem.Solid-State Lett.,2009,12(4):J44-J46.
[17]WAKO A H,DEJENE B F,SWART H C.Roles of doping ions in afterglow properties of blue Ca Al2O4∶Eu2+,Nd3+phosphors[J].Phys.B,2014,439:153-159.
[18]MLLER M,VOLHARD M F,JSTEL T.Photoluminescence and afterglow of deep red emitting Sr Sc2O4∶Eu2+[J].RSCAdv.,2016,6(10):8483-8488.
[19]MERONI D,PORATI L,DEMARTIN F,et al..Sol-gel synthesis of Ca Ti O3∶Pr3+red phosphors:tailoring the synthetic parameters for luminescent and afterglow applications[J].ACS Omega,2017,2(8):4972-4981.
[20]ZHUANG Y X,UEDA J,TANABE S.Photochromism and white long-lasting persistent luminescence in Bi3+-doped ZnGa2O4ceramics[J].Opt.Mater.Express,2012,2(10):1378-1383.
[21]JIN Y,BAI Y M,GE M Q.Preparation and luminescence properties of a white emitting long afterglow luminous fiber based on FRET[J].J.Rare Earths,2016,34(4):374-380.
[22]申凤娟,夏继宏,程正富.长余辉荧光粉的研究进展[J].中国照明电器,2016(11):9-15.SHEN F J,XIA J H,CHENG Z F.Progress of research on the long afterglow phosphors[J].China Light Lighting,2016(11):9-15.(in Chinese)
[23]张秋函,谭慧英,刘永冲,等.纳米纤维状Sr3Al2O5Cl2∶Eu2+,Tm3+的白色长余辉性能[J].发光学报,2017,38(6):697-701.ZHANG Q H,TAN H Y,LIU Y C,et al..White long persistent phenomenon from Sr3Al2O5Cl2∶Eu2+,Tm3+nano-fiber[J].Chin.J.Lumin.,2017,38(6):697-701.(in Chinese)
[24]郑升辉,刘亚楠,李月婵,等.Sm3+掺杂对Sr La Ga3O7自身长余辉发光性质的影响[J].发光学报,2018,39(3):287-292.ZHENG S H,LIU Y N,LI Y C,et al..Effect of doping Sm3+on long afterglow properties of Sr La Ga3O7[J].Chin.J.Lumin.,2018,39(3):287-292.(in Chinese)
[25]ABDUKAYUM A,CHEN J T,ZHAO Q,et al..Functional near infrared-emitting Cr3+/Pr3+co-doped zinc gallogermanate persistent luminescent nanoparticles with superlong afterglow for in vivo targeted bioimaging[J].J.Am.Chem.Soc.,2013,135(38):14125-14133.
[26]WAN M H,WANG Y H,WANG X S,et al..The properties of a novel green long afterglow phosphor Zn2Ge O4∶Mn2+,Pr3+[J].Opt.Mater.,2014,36(3):650-654.
[27]SINGH S K.Red and near infrared persistent luminescence nano-probes for bioimaging and targeting applications[J].RSC Adv.,2014,4(102):58674-58698.
[28]BAKLANOVA Y V,ENYASHIN A N,MAKSIMOVA L G,et al..Sensitized IR luminescence in Ca3Y2Ge3O12∶Nd3+,Ho3+under 808 nm laser excitation[J].Ceram.Int.,2018,44(6):6959-6967.
[29]TAKEMOTO M,ISEKI T.Fluorescence and afterglow of Ca2Sn2Al2O9∶Mn2+[J].J.Phys.Chem.Solids,2018,114:88-93.
[30]过诚,丛妍,董斌,等.(Zn1-x,Mgx)2Ge O4∶Mn2+的荧光以及长余辉发光性能[J].发光学报,2017,38(9):161-1166.GUO C,CONG Y,DONG B,et al..Photoluminescence and long-lasting phosphorescence characteristics of(Zn1-x,Mgx)2Ge O4∶Mn2+[J].Chin.J.Lumin.,2017,38(9):1161-1166.(in Chinese)
[31]MJAKIN S V,MINAKOVA T S,BAKHMETYEV V V,et al..Effect of the surfaces of Zn3(PO4)2∶Mn2+phosphors on their luminescent properties[J].Russ.J.Phys.Chem.A,2016,90(1):240-245.
[32]SUN X Y,HE Z,GU X.Tunable luminescence for KNa Ca2(PO4)2∶Eu2+/Mn2+phosphors due to energy transfer from Eu2+to Mn2+[J].J.Mater.Sci.Mater.Electron.,2018,29(8):6961-6965.