NaYF_(4)∶Yb^(3+)/Eu^(3+)上转换发光微纳粒子在防伪识别中的应用研究  

Application and Research of NaYF_(4)∶Yb^(3+)/Eu^(3+)Upconverting Luminescent Micro-Nano Particles in Anti-Counterfeiting Identification

作　　者：王翀 磨建业 李冬冬 佘江波[2] 刘震 WANG Chong;MO Jian-ye;LI Dong-dong;SHE Jiang-bo;LIU Zhen(School of Electronic Engineering,Xi’an University of Posts and Telecommunications,Xi’an 710121,China;State Key Laboratory of Transient Optics and Photonics,Xi’an Institute of Optics and Precision Mechanics,Chinese Academy of Sciences,Xi’an 710119,China)

机构地区：[1]西安邮电大学电子工程学院,陕西西安710121 [2]中国科学院西安光学精密机械研究所瞬态光学与光子技术国家重点实验室,陕西西安710119

出　　处：《光谱学与光谱分析》2021年第5期1525-1529,共5页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(61805199);陕西省自然科学基础研究计划项目(2019JQ-863);陕西省自然科学基金(2020JM-578);陕西省教育厅专项科研计划项目(18JK0707)资助。

摘　　要：稀土掺杂上转换发光微纳粒子在防伪识别方面有着巨大的应用前景。首先采用水热合成法制备了NaYF_(4)∶Yb^(3+)/Eu^(3+)微纳粒子,通过X射线衍射(XRD)、扫描电子显微镜(SEM)及透射电子显微镜(TEM)对NaYF_(4)∶Yb^(3+)/Eu^(3+)微纳粒子的尺寸、形貌和结晶度等方面进行了研究,同时使用980 nm的泵浦源对NaYF_(4)∶Yb^(3+)/Eu^(3+)微纳粒子的发光性能进行了分析;其次将NaYF_(4)∶Yb^(3+)/Eu^(3+)微纳粒子与酒精按一定比例混合制成丝网印刷剂,结合网络定制的丝网模版在纸上印制了不同字样的防伪图案,风干后将字样暴露在980 nm的激光辐照下,并使用相机对其进行成像研究;最后将印制的字样分成两部分,一部分保存在室内25℃恒温环境下,另外一部分保存在冬季一月份室外自然环境下,保存地点均为西安市,一周后对不同环境下的字样再次使用完全相同的实验仪器进行成像测试。实验及测试结果显示,NaYF_(4)∶Yb^(3+)/Eu^(3+)微纳粒子与NaYF 4标准卡的衍射峰完全一致,没有其他杂质产生;实验合成的微纳粒子外形均为六方体,且平均长度和横截宽度分别为209和175 nm,微纳晶体表面光滑、无缺陷、未弯曲、结晶度较高、分散性较好,电子衍射环与NaYF_(4)∶Yb^(3+)/Eu^(3+)微纳粒子的312,300和302晶面相对应;NaYF_(4)∶Yb^(3+)/Eu^(3+)微纳粒子受掺杂离子的影响,在不同的能级跃迁下分别产生蓝、绿、黄、红四种可见光,通过对NaYF_(4)∶Yb^(3+)/Eu^(3+)微纳粒子荧光光谱分析,Eu 3+非对称性比率约为1,表明磁偶极子跃迁与电偶极子跃迁相当;NaYF_(4)∶Yb^(3+)/Eu^(3+)微纳粒子制成的丝网印刷剂在不同环境下成像结果良好均清晰可见、容易辨识,但受存放环境影响,室内成像结果与最初的成像结果相比变化不大,室外所有成像字符受到自然环境下水汽的影响,亮度均略有下降,但仍能识别。成像结果表明,所制备的NaYF_(4)∶Yb^(3+)/ERare earth doped upconversion luminescent micro-nano particles have great application prospects in anti-counterfeit identification.First of all,in the article NaYF_(4)∶Yb^(3+)/Eu^(3+)micro-nano particles prepared by hydrothermal synthesis method,The size,morphology and crystallinity of NaYF_(4)∶Yb^(3+)/Eu^(3+)micro-nano particles were investigated by X-ray diffraction(XRD)、scanning electron microscope(SEM)and transmission electron microscope,and the luminescence properties of NaYF_(4)∶Yb^(3+)/Eu^(3+)micro-nano particles were analyzed using a 980 nm pump source;Secondly,NaYF_(4)∶Yb^(3+)/Eu^(3+)micro-nano particles and alcohol were mixed in a certain proportion to make a screen printing agent and combined with a networkcustomized screen template,different anti-counterfeit patterns were printed on the paper.After air drying,the words were exposed to a 980 nm laser and camera were used to study it.Finally,the printed words were divided into two parts,one was stored indoors at a constant temperature of 25℃,and the other was stored in the outdoor natural environment in January in winter.The storage locations are all Xi’an.After one week,in different environments the words were again tested with the same experimental instruments for imaging.The experiment and test results show that the diffraction peak of NaYF_(4)∶Yb^(3+)/Eu^(3+)micronano particles is a completely consistent standard card of NaYF4,and no other impurities are generated.In this experiment,The synthesized micro-nano particles are all hexagonal in shape,and the average length and cross-sectional width are 209 and 175 nm respectively.The surface of the nanocrystal is smooth,defect-free,unbent,with high crystallinity and good dispersion.The electron diffraction ring corresponds to the 312,300,and 302 crystal planes of NaYF_(4)∶Yb^(3+)/Eu^(3+)micro-nano particles.NaYF_(4)∶Yb^(3+)/Eu^(3+)micro-nano particles are affected by doped ions,it produces four visible lights of blue,green,yellow and red by different energy level transitions.Through f

关 键 词：上转换发光 水热合成法 防伪识别 丝网印刷 微纳粒子 

分 类 号：TQ422[化学工程]