大气环境下合成白光发射的Tb^(3+)/Eu^(3+)共掺杂全无机卤化物钙钛矿量子点

White Lght Emission from the Tb^(3+)/Eu^(3+) Co-doped All-inorganic Halide Perovskite Quantum Dots in Ambient Air

为克服因混合不同卤化物钙钛矿量子点发生阴离子交换反应、不稳定的红光发射卤化物钙钛矿量子点等而导致在获取白光发射方面存在的不足,提出了一种可以在大气环境下合成Tb^(3+),Eu^(3+)稀土离子共掺杂全无机卤化物钙钛矿量子点的方法。调节Tb^(3+),Eu^(3+)稀土离子的掺杂比例,调控从钙钛矿量子点主晶格到Tb^(3+)和Eu^(3+)离子的能量转移,获得了单一组分、白光发射的钙钛矿量子点(Tb,Eu):CsPbCl3和(Tb,Eu):CsPb(Cl/Br)3,并对量子点的形貌、结构、发光性能及能量传递机理和稳定性进行了详细研究。研究结果表明:在365nm激光激发下,不同含量Tb^(3+)/Eu^(3+)离子共掺杂的钙钛矿量子点(Tb,Eu):CsPbCl3发射光谱对应的色坐标位于1931色度图中的白光区域。在进料比PbCl2∶TbCl3∶EuCl3为1∶1.5∶1时,量子产率为3.59%,比纯的CsPbCl3量子点的量子产率(0.57%)提高了6倍。进一步研究发现,该(Tb,Eu):CsPbCl3量子点在空气中储存2个月之后,量子产率几乎保持不变(3.63%),保持了良好的稳定性。此外,研究了采用不同溶剂(正辛烷、十八烯)合成Tb^(3+)/Eu^(3+)共掺杂钙钛矿量子点的发光特性。Tb^(3+)/Eu^(3+)离子共掺杂的钙钛矿量子点(Tb,Eu):CsPbCl3可实现单一组分的白光发射,有良好的稳定性,具备一定的应用前景。

In order to overcome the shortcomings in obtaining white light emission due to the anion exchange reaction from different halide perovskite quantum dots and unstable red light emission halide perovskite quantum dots,a method was used to prepare rare earth ions Tb^(3+)/Eu^(3+)co-doping into perovskite quantum dots in ambient air.By adjusting the doping ratio of Tb^(3+)/Eu^(3+)rare earth ions,the energy transfer from the host lattice of perovskite quantum dots to Tb^(3+)/Eu^(3+)was accordingly manipulated to obtain single-component and white light emission perovskite quantum dots of(Tb,Eu)∶CsPbCl3 and(Tb,Eu)∶CsPb(Cl/Br)3.Meanwhile,we delicately investigated the morphology,structure,luminescence performance,energy transfer mechanism and stability of quantum dots.The results show that under 365 nm laser excitation,white light emission with 1931 Commission Internationale de l’Eclairage color coordinates was achieved in perovskite quantum dots(Tb,Eu):CsPbCl3 with different contents of Tb^(3+)/Eu^(3+)ions.When the feed ratio PbCl2∶TbCl3∶EuCl3 is 1∶1.5∶1,the quantum yield is 3.59%,which is 6 times higher than the quantum yield(0.57%)of pure CsPbCl3 quantum dots.Further research found that the(Tb,Eu)∶CsPbCl3 quantum dots were stored in the air for 2 months,the quantum yield was almost unchanged(3.63%),maintaining good stability.Moreover,the luminescence characteristics of the co-doped perovskite quantum dots with Tb^(3+)and Eu^(3+)synthesized with different solvents(n-octane,1-octadecene)were compared.Tb^(3+)/Eu^(3+)co-doped perovskite quantum dots(Tb,Eu):CsPbCl3 ware used to achieve single-component white light emission with good stability and has certain application prospects.