Calabro Rosemary L, Karna Priya, Kim Doo Young, Yang Dong-Sheng
Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055, USA.
J Chem Phys. 2020 Aug 14;153(6):064701. doi: 10.1063/5.0021011.
Upconverting nanoparticles (UCNPs) composed of NaYF and doped with photoactive Yb and Er (NaYF:Yb/Er) are highly desirable for many biological applications, but obtaining stable dispersions of UCNPs is challenging. Traditional synthetic methods often use complicated synthetic steps, produce toxic side products, and require post modifications to make UCNPs more dispersible in aqueous solutions. In this study, we demonstrate that laser ablation in liquid (LAL) is a novel approach to synthesize water-dispersible and -stable UCNPs with advantages of particle-size tuning, in situ coating of UCNPs with capping agents, no use of toxic or high boiling point solvents, and short reaction times. NaYF:Yb/Er UCNPs were produced through LAL of annealed targets using water as the liquid, and their compositions and properties were investigated at a laser fluence of 0.57 J cm-6.22 J cm by direct capping with citric acid and ethylene glycol and by comparing with the UCNPs prepared from the traditional hydrothermal method. Low laser fluences produced polydisperse particles consisting of no photoactive species through a thermal evaporation mechanism, while high laser fluences generated UCNPs with more uniform morphologies and compositions similar to the target material by an explosive ejection mechanism. The inclusion of capping agents during LAL allowed for direct coating of the UCNP surface without the need of post modifications, and the concentrations of capping agents affected the UCNP photoluminescence lifetimes. As compared to the hydrothermal method, the LAL-prepared samples showed better size control and no degradation of the capping agents.
由NaYF组成并掺杂有光活性Yb和Er(NaYF:Yb/Er)的上转换纳米颗粒(UCNPs)在许多生物应用中非常理想,但获得UCNPs的稳定分散体具有挑战性。传统的合成方法通常使用复杂的合成步骤,产生有毒副产物,并且需要进行后处理以使UCNPs在水溶液中更易分散。在本研究中,我们证明了液体中的激光烧蚀(LAL)是一种合成水分散性和稳定性UCNPs的新方法,具有粒径调节、用封端剂原位包覆UCNPs、不使用有毒或高沸点溶剂以及反应时间短等优点。通过以水为液体对退火靶材进行LAL制备了NaYF:Yb/Er UCNPs,并通过用柠檬酸和乙二醇直接封端并与传统水热法制备的UCNPs进行比较,在0.57 J cm-6.22 J cm的激光能量密度下研究了它们的组成和性质。低激光能量密度通过热蒸发机制产生由无活性光物种组成的多分散颗粒,而高激光能量密度通过爆炸喷射机制产生具有更均匀形态和与靶材相似组成的UCNPs。在LAL过程中加入封端剂可以直接包覆UCNP表面而无需后处理,并且封端剂的浓度影响UCNP的光致发光寿命。与水热法相比,LAL制备的样品显示出更好的尺寸控制且封端剂无降解。