硅酸盐学报2024，Vol.52Issue(8)：2455-2462,8.DOI:10.14062/j.issn.0454-5648.20230895
三维立体显示用稀土掺杂纯红色上转换发光氟氧化物玻璃陶瓷
Rare-Earth Doped Pure Red Upconversion Luminescent Oxyfluoride Glass Ceramics for Three-Dimensional Stereoscopic Displays
摘要
Abstract
Introduction With the development of society,two-dimensional displays can no longer meet people's needs.Three-dimensional displays can completely reproduce the scene of world,showing the depth of the object,the sense of hierarchy,and reality because the real world is also three-dimensional.At present,there are a lot of techniques to realize three-dimensional displays,including two-dimensional analog three-dimensional displays,binocular parallax stereoscopic displays,and three-dimensional stereoscopic displays.Nevertheless,two-dimensional simulation three-dimensional display does not produce physical depth of field;Binocular parallax stereoscopic display is limited because of the disadvantages of small angle zoom,causing visual fatigue,and needing to assistant equipment.In contrast,three-dimensional stereoscopic display technology has attracted attention due to its realistic display effect,real-time interaction,and multi-angle observation.Among the related technologies,the static volume display technology based on transparent upconversion luminescent materials shows the most significant advantages. Methods Appropriate composition design is a necessary condition for the nucleation and growth of fluoride nanocrystals in glass.In this study,rare earth doped pure red upconversion luminescent oxyfluoride transparent glass ceramics were obtained via the conventional melt-quenching-thermal annealing method.The glass compositions(in mole)are 60SiO2-6Al2O3-7Na2CO3-19NaF-xErF3-yTmF3-(8-x-y)YF3(x=0-1.6%,y=0-0.4%).The raw materials are SiO2,Al2O3,Na2CO3(Sinopharm Chemical Reagents Co.,Ltd.),and high-purity NaF,ErF3,TmF3,YF3(Shanghai Macklin Biochemical Technology Co.,Ltd),which were weighed,mixed and ground in an agate mortar.The obtained mixtures were then placed in a sealed alumina crucible and melted at 1 550℃ for 45 min under ambient atmosphere.Subsequently,the glass melt was poured into a 200℃ preheated copper mould and annealed at 400℃ for 5 h to relinquish the internal stress.Finally,the obtained bulk glass was heat-treated at 650℃ for 2 h to induce in-situ fluoride crystallization inside the glass to obtain oxyfluoride glass ceramics containing NaYF4 nanocrystals(NaYF4@glass). Results and discussion For Er3+/Tm3+co-doped NaYF4@glass,the influence of Er3+doped content was explored and an optimal Er3+concentration of 15%was confirmed.Meanwhile,with the increase of co-doped Tm3+content,the red emission of Er3+gradually enhanced due to the energy transfer process between Er3+and Tm3+.Correspondingly,the color purity of red emission increased to realize the pure red emission upon the 980 nm near-infrared laser excitation.In addition,the temperature dependent spectra(from 80 K to 470 K)of 15%Er-2%Tm:NaYF4@glass were tested.Owing to the electrons at the 2H11/2,4S3/2 and 4F9/2 levels of Er3+were populated independently,there was no direct temperatures-dependent electron correlation between the green(2H11/2,4S3/2)and red(4F9/2)levels of Er3+ions.With the increase of temperature,the shape of the emission peak remained basically unvaried,indicating excellent chromatic stability.Ultimately,the Er3+/Tm3+co-doped NaYF4@glass-based three-dimensional prototype display device showed three-dimensional static/dynamic designed red patterns with high color purity and high stability,providing its potential use in new-generation three-dimensional stereoscopic display technology. Conclusions In summary,Er3+/Tm3+co-doped NaYF4@glass can be successfully prepared via conventional melt-quenching-thermal annealing method.The optimized 15%Er-2%Tm co-doped NaYF4@glass can achieve pure red upconversion luminescence due to the energy transfer process between Er3+and Tm3+.Owing to that the electrons in the 2H11/2,4S3/2 and 4F9/2 levels of Er3+are independently populated,there is not direct temperature-dependent electron correlation between the green energy level(2H11/2,4S3/2)and the red energy level(4F9/2)of Er3+.Moreover,the Er3+/Tm3+co-doped NaYF4@glass-based three-dimensional prototype display device is constructured.This study can provide a new idea for the development of pure color transparent upconversion materials for three-dimensional stereoscopic display.关键词
三维立体显示/上转换发光材料/稀土离子/氟氧化物玻璃陶瓷Key words
three-dimensional stereoscopic displays/upconversion materials/rare earth/oxyfluoride glass ceramics分类
化学化工引用本文复制引用
尤凤銮,王少雄,郑嵩,张年丰,林世盛,陈大钦..三维立体显示用稀土掺杂纯红色上转换发光氟氧化物玻璃陶瓷[J].硅酸盐学报,2024,52(8):2455-2462,8.基金项目
国家自然科学基金(52272141,51972060,12074068,52102159,22103013,12304442) （52272141,51972060,12074068,52102159,22103013,12304442）
福建省自然科学基金(2022J05091,2020J02017,2021J06021,2021J01190,2020J01931,2020H0026). （2022J05091,2020J02017,2021J06021,2021J01190,2020J01931,2020H0026）
