陶瓷学报2025，Vol.46Issue(5)：959-970,12.DOI:10.13957/j.cnki.tcxb.2025.05.010
双钙钛矿Cs2Na0.9Ag0.1In1-xZrxCl6的制备及其可调谐黄—白—蓝三色自陷激子发光研究
Tunable Yellow-white-blue Self-trapped Exciton Emissions of Double Perovskites Cs2Na0.9Ag0.1In1-xZrxCl6
摘要
Abstract
[Background and purposes]Double perovskite materials exhibit broad application prospects in light-emitting diodes(LEDs),optical anti-counterfeiting,and display technologies,due to their exceptional optoelectronic properties.However,conventional double perovskite phosphors still face several challenges in practical applications,such as energy loss caused by the reabsorption effect in multi-component phosphors,stability issues arising from differential aging rates among components,and limitations in large-scale production due to complex synthesis processes.Additionally,single-component double perovskite materials(LHDPs)often struggle to achieve broad-spectrum tunable emission,restricting their utility in multicolor luminescence and white-light LEDs.To address these challenges,an innovative Zr4+doping strategy was proposed,aiming at modulating the crystal structure and electronic band structure of Cs2Na0.9Ag0.1InCl6 double perovskites to achieve efficient single-component broadband emission.Specific objectives include:(1)optimizing the bandgap structure via Zr4+doping to enhance exciton localization,(2)revealing the regulatory mechanism of Zr4+on dual emission channels of self-trapped excitons(STEs)and(3)developing phosphors with high photoluminescence quantum yield(PLQY)and tunable correlated color temperature(CCT)for applications in white-light LEDs and optical anti-counterfeiting. [Methods]A series of Cs2Na0.9Ag0.1InCl6 double perovskite phosphors with varying Zr4+concentrations(0%-100%)were synthesized by using chemical coprecipitation method.Morphology and elemental distribution were characterized using scanning electron microscopy(SEM)and energy-dispersive X-ray spectroscopy(EDS),confirming uniform micron-sized octahedral structures.X-ray diffraction(XRD)analysis revealed a highly crystalline face-centered cubic structure,with diffraction peaks shifting toward higher angles as,Zr4+concentration was increased,indicating lattice contraction.Raman spectroscopy and X-ray photoelectron spectroscopy(XPS)were employed to study the influence of Zr4+on the electronic structure.Optical properties were systematically evaluated using UV-Vis absorption and photoluminescence(PL)spectroscopy,complemented by temperature-dependent PL 80-320 K)and fluorescence lifetime analysis to elucidate the luminescence dynamics.Notably,tunability of the emission color was explored by varying excitation wavelengths(254-360 nm)and Zr4+doping levels,with chromaticity coordinates(CIE)and CCT calculated for each condition. [Results]Zr4+successfully substituted In3+/(Ag+/Na+)sites,forming stable[ZrCl6]2⁻ octahedra,which induced lattice distortion and electron cloud rearrangement.A significant enhancement in the[ZrCl6]2⁻ absorption band at 254 nm was observed with increasing content of Zr4+,while PL spectra exhibited dual-peak emission(blue and yellow),confirming the establishment of dual-channel STE1(yellow)and STE2(blue)emission mechanisms.Under optimized conditions(Zr4+=40%),the material achieved a PLQY of 86.9%under 334 nm excitation.Under 254 nm excitation,competitive blue-yellow emission yielded standard white light(CIE:0.28,0.36)with a PLQY of 70.6%and tunable CCT(4000-10000 K).Temperature-dependent PL analysis demonstrated excellent thermal stability(Eb=100.992 meV),while lifetime measurements indicated prolonged exciton recombination due to Zr4+doping,effectively suppressing non-radiative decay. [Conclusions]Precise control over dual STE emission channels in Cs2Na0.9Ag0.1InCl6 double perovskites via Zr4+doping was demonstrated,overcoming the limitation of non-tunable emission in single-component materials.Zr4+incorporation not only activated blue emission through lattice distortion but also enhanced the radiative efficiency via exciton localization.The optimized phosphors exhibited outstanding performance,including high PLQY(≈86%)and tunable white-light emission(CCT=4000-10000 K),thus offering a novel material platform for next-generation optical anti-counterfeiting and white-light LEDs.Future research may focus on multi-metal co-doping to further manipulate STE dynamics and expand optoelectronic applications.关键词
无铅双钙钛矿/自陷激子/多色发光调控Key words
lead-free double perovskite/self-trapped excitons/multicolor luminescence tuning分类
化学化工引用本文复制引用
吴蓓,李卫洁,周蓓莹,叶佳意,王连军,江莞..双钙钛矿Cs2Na0.9Ag0.1In1-xZrxCl6的制备及其可调谐黄—白—蓝三色自陷激子发光研究[J].陶瓷学报,2025,46(5):959-970,12.基金项目
国家自然科学基金(52472067,U23A20564) （52472067,U23A20564）
上海市自然科学基金(23ZR1402700). （23ZR1402700）
