Sr_2Si_5N_(8-δ)C_x:Eu~(2+)碳氮化物荧光粉的制备及发光性能研究
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摘要
采用高温固相法成功制备了Sr_2Si_5N_(8-δ)C_x:Eu~(2+)碳氮化物荧光粉,并研究了Si-C替代Si-N对晶体结构和发光性能的影响。XRD结果表明,部分Si-C替代Si-N并未改变荧光粉的晶体结构,C4-替代N3-最大掺杂量不超过x=1.2。荧光光谱结果表明,荧光粉的激发和发射光谱并未随着x值增加而发生偏移,意味着Si-C替代Si-N对Eu2+周围晶体场环境影响较小;当x=0.3时,荧光粉的发光强度达到最大,随着x值进一步增大,样品结晶性变差,导致其发光强度降低。荧光粉热猝灭性能结果表明,适量的Si-C替代Si-N能够提升样品的热猝灭性能;热猝灭性能提升机制主要采用离子半径错配模型进行解释。
Sr_2Si_5N_(8-δ)C_x:Eu~(2+) carbonitride phosphors were synthesized by the high temperature solid-state reaction.The influence of Si-C substituting Si-N bond on the crystal structure and the luminescence properties were investigated.XRD results showed that the crystal structure is not changed when partial Si-C replacing Si-N bond.The maximum doping amount for C~(4-)substitution of N~(3-) ions is not more than x=1.2.Photoluminescence(PL) spectra showed that the excitation and emission spectra do not shift with increasing x values,indicating that the substitution of Si-N for Si-C has little influence on the crystal field around Eu~(2+).When x=0.3,the PL intensity reaches the maximum value.As increasing x values,the PL intensity decreases due to the worse crystalline.The results of thermal quenching properties showed that moderate Si-C replacing Si-N bond could enhance the thermal quenching properties.The enhancement mechanism of the thermal quenching properties is proposed based on the Size-Mismatch model.
Sr_2Si_5N_(8-δ)C_x:Eu~(2+) carbonitride phosphors were synthesized by the high temperature solid-state reaction.The influence of Si-C substituting Si-N bond on the crystal structure and the luminescence properties were investigated.XRD results showed that the crystal structure is not changed when partial Si-C replacing Si-N bond.The maximum doping amount for C~(4-)substitution of N~(3-) ions is not more than x=1.2.Photoluminescence(PL) spectra showed that the excitation and emission spectra do not shift with increasing x values,indicating that the substitution of Si-N for Si-C has little influence on the crystal field around Eu~(2+).When x=0.3,the PL intensity reaches the maximum value.As increasing x values,the PL intensity decreases due to the worse crystalline.The results of thermal quenching properties showed that moderate Si-C replacing Si-N bond could enhance the thermal quenching properties.The enhancement mechanism of the thermal quenching properties is proposed based on the Size-Mismatch model.
引文
[1]Yam F K,Hassan Z.Innovative advances in LED technology[J].Microelectr.J.,2005,36:129.
[2]Pimputkar S,Speck J S,Den Baars S P.Prospects for LED lighting[J].Nat.Photonics,2009,23:180.
[3]魏绍娟,邾强强,季巍巍,郝绿原,徐鑫.Si-N共掺杂Lu3Al5O12:Ce荧光粉的制备及荧光性质[J].中国稀土学报,2016,34:524.Wei S J,Zhu Q Q,Ji W W,Hao L Y,Xu X.Synthesis and photoluminescence properties of Lu3Al5O12:Ce phosphor[J].Journal of Chinese Sciety of Rare Earths,2016,34:524.
[4]孙文周,陈宇红.燃烧法合成Sr3Al2O6:Eu2+,Dy3+发光材料的物相组成研究[J].中国稀土学报,2016,34:538.Sun W Z,Chen Y H.Phase compositions of phosphors Sr3Al2O6:Eu2+,Dy3+synthesized by combustion synthesis method[J].Journal of Chinese Sciety of Rare Earths,2016,34:538.
[5]张梅,何鑫,丁维嘉,王静.白光LED用氮氧化合物荧光粉[J].化学进展,2010,22:376.Zhang M,He X,Ding W J,Wang J.Oxynitride and nitride phosphors for white LEDs[J].Progress in Chemistry,2010,22:376.
[6]赵昕冉,傅仁利,宋秀峰,张绍东,潘政薇.白光LED用硅基氮(氧)化物荧光转换材料的研究进展[J].硅酸盐通报,2009,5(28):965.Zhao X R,Fu R L,Song X F,Zhang S D,Pan Z W.Research progress in silicon-based(oxy)nitride phosphors for white LED[J].Bulletin of the Chinese Ceramic Society,2009,5(28):965.
[7]Ronda C R,Jüstel T,Nikol H.Rare earth phosphors:fundamental and applications[J].J.Alloys Compd.,1998,275:669.
[8]Liu H L,He D W,Shen F.Luminescence properties of green-emitting phosphor(Ba1-x,Srx)2Si O4:Eu for white LEDS[J].J.Rare Earths,2006,24(1):121.
[9]Piao X Q,Machida K,Horikawa T.Acetate reduction synthesis of Sr2Si5N8:Eu phosphor and its luminescenceproperties[J].J.Lumin.,2010,130:8.
[10]Watanabe H,Kijima N.Crystal structure and luminescence properties of SrxCa1-xAl Si N3:Eu mixed nitride phosphors[J].J.Alloys Compd.,2009,475:434.
[11]Li Y Q,De With G,Hintzen H T.The effect of replacement of Sr by Ca onthe structural and luminescence properties of the red-emitting Sr2Si5N8:Eu LED conversion phosphor[J].J.Solid State Chem.,2008,181:515.
[12]Zeuner M,Hintze F,Schnick W.Low temperature precursor route for highly efficient spherically shaped LED-phosphors Sr2Si5N8:Eu(M=Eu,Sr,Ba)[J].Chem.Mate.,2009,21:336.
[13]Lei B F,Machida K,Horikawa T,et al.Synthesis and photoluminescence properties of Ca Al Si N3:Eu nanocrystals[J].Chem.Lett.,2010,39:104.
[14]Zhang H C,Horikawa T,Machida K.Preparation,structrure and luminescence properties of Y2Si4N6C:Ce and Y2Si4N6C:Tb3+[J].J.Elec.Soc.,2006,153(7):H151.
[15]Liddell K,Thompson D P,Teat S J.M2(Si,Al)4(N,C)7(M=La,Y,Ca)carbonitrides II.The crystal structure of Ca0.8Y1.2Si4N6.8C0.2[J].J.Euro.Cera.Soc.,2005,25:49.
[16]Huang W Y,Yoshimura F,Uedd K,Pang W K,Su B J,Jang L Y,Chiang C Y,Zhou W,Duy N H,Liu R S.Domination of second-sphere shrinkage effect to improve photoluminescence of red nitride phosphors[J].Inorg.Chem.,2014,53:12822.
[17]Zhang H C,Horikawa T,Machida K.Preparation,structrure and luminescence properties of Y2Si4N6C:Ce and Y2Si4N6C:Tb3+[J].J.Elec.Soc.,2006,153(7):H151.
[18]Chen W T,Sheu H S,Liu R S.Cation-size-mismatch tuning of photoluminescence in oxynitride phosphors[J].J.Am.Chem.Soc.,2012,134:8022.
[19]Xie R J,Li Y Q,Hirosaki N.Nitride Phosphor and Solid-State Lighting[M].New York:Taylor&Francis,2011.
[2]Pimputkar S,Speck J S,Den Baars S P.Prospects for LED lighting[J].Nat.Photonics,2009,23:180.
[3]魏绍娟,邾强强,季巍巍,郝绿原,徐鑫.Si-N共掺杂Lu3Al5O12:Ce荧光粉的制备及荧光性质[J].中国稀土学报,2016,34:524.Wei S J,Zhu Q Q,Ji W W,Hao L Y,Xu X.Synthesis and photoluminescence properties of Lu3Al5O12:Ce phosphor[J].Journal of Chinese Sciety of Rare Earths,2016,34:524.
[4]孙文周,陈宇红.燃烧法合成Sr3Al2O6:Eu2+,Dy3+发光材料的物相组成研究[J].中国稀土学报,2016,34:538.Sun W Z,Chen Y H.Phase compositions of phosphors Sr3Al2O6:Eu2+,Dy3+synthesized by combustion synthesis method[J].Journal of Chinese Sciety of Rare Earths,2016,34:538.
[5]张梅,何鑫,丁维嘉,王静.白光LED用氮氧化合物荧光粉[J].化学进展,2010,22:376.Zhang M,He X,Ding W J,Wang J.Oxynitride and nitride phosphors for white LEDs[J].Progress in Chemistry,2010,22:376.
[6]赵昕冉,傅仁利,宋秀峰,张绍东,潘政薇.白光LED用硅基氮(氧)化物荧光转换材料的研究进展[J].硅酸盐通报,2009,5(28):965.Zhao X R,Fu R L,Song X F,Zhang S D,Pan Z W.Research progress in silicon-based(oxy)nitride phosphors for white LED[J].Bulletin of the Chinese Ceramic Society,2009,5(28):965.
[7]Ronda C R,Jüstel T,Nikol H.Rare earth phosphors:fundamental and applications[J].J.Alloys Compd.,1998,275:669.
[8]Liu H L,He D W,Shen F.Luminescence properties of green-emitting phosphor(Ba1-x,Srx)2Si O4:Eu for white LEDS[J].J.Rare Earths,2006,24(1):121.
[9]Piao X Q,Machida K,Horikawa T.Acetate reduction synthesis of Sr2Si5N8:Eu phosphor and its luminescenceproperties[J].J.Lumin.,2010,130:8.
[10]Watanabe H,Kijima N.Crystal structure and luminescence properties of SrxCa1-xAl Si N3:Eu mixed nitride phosphors[J].J.Alloys Compd.,2009,475:434.
[11]Li Y Q,De With G,Hintzen H T.The effect of replacement of Sr by Ca onthe structural and luminescence properties of the red-emitting Sr2Si5N8:Eu LED conversion phosphor[J].J.Solid State Chem.,2008,181:515.
[12]Zeuner M,Hintze F,Schnick W.Low temperature precursor route for highly efficient spherically shaped LED-phosphors Sr2Si5N8:Eu(M=Eu,Sr,Ba)[J].Chem.Mate.,2009,21:336.
[13]Lei B F,Machida K,Horikawa T,et al.Synthesis and photoluminescence properties of Ca Al Si N3:Eu nanocrystals[J].Chem.Lett.,2010,39:104.
[14]Zhang H C,Horikawa T,Machida K.Preparation,structrure and luminescence properties of Y2Si4N6C:Ce and Y2Si4N6C:Tb3+[J].J.Elec.Soc.,2006,153(7):H151.
[15]Liddell K,Thompson D P,Teat S J.M2(Si,Al)4(N,C)7(M=La,Y,Ca)carbonitrides II.The crystal structure of Ca0.8Y1.2Si4N6.8C0.2[J].J.Euro.Cera.Soc.,2005,25:49.
[16]Huang W Y,Yoshimura F,Uedd K,Pang W K,Su B J,Jang L Y,Chiang C Y,Zhou W,Duy N H,Liu R S.Domination of second-sphere shrinkage effect to improve photoluminescence of red nitride phosphors[J].Inorg.Chem.,2014,53:12822.
[17]Zhang H C,Horikawa T,Machida K.Preparation,structrure and luminescence properties of Y2Si4N6C:Ce and Y2Si4N6C:Tb3+[J].J.Elec.Soc.,2006,153(7):H151.
[18]Chen W T,Sheu H S,Liu R S.Cation-size-mismatch tuning of photoluminescence in oxynitride phosphors[J].J.Am.Chem.Soc.,2012,134:8022.
[19]Xie R J,Li Y Q,Hirosaki N.Nitride Phosphor and Solid-State Lighting[M].New York:Taylor&Francis,2011.