Manipulation of up-conversion emission in NaYF4 core@shell nanoparticles doped by Er3+, Tm3+, or Yb3+ ions by excitation wavelength—three ions—plenty of possibilities

Abstract

Nanoparticles (NPs) based on host compound NaYF₄ with core@shell structures were synthesised by the precipitation reaction in high-boiling point octadecene/oleic acid solvent. Four laser wavelengths were used (808, 975, 1208, or 1532 nm) for excitation of the obtained NPs. The resulting emission and mechanisms responsible for spectroscopic properties were studied in detail. Depending on NP compositions, i.e. type of doping ion (Er³⁺, Tm³⁺, or Yb³⁺) or presence of dopants in the same or different phases, adjustable up-conversion (UC) could be obtained with emission peaks covering the visible to near-infrared range (475 to 1625 nm). The presented results demonstrated multifunctionality of the prepared NPs. NaYF₄:2%Tm³⁺@NaYF₄ NPs exhibited emission at 700 and 1450 nm under 808 nm laser excitation or 800 and 1625 nm emission under 1208 nm laser radiation, as a result of ground- and excited-state absorption processes (GSA and ESA, respectively). However, NaYF₄:5%Er³⁺,2%Tm³⁺@NaYF₄ NPs showed the most interesting properties, as they can convert all studied laser wavelengths due to the absorption of Tm³⁺ (808, 1208 nm) or Er³⁺ ions (808, 975, 1532 nm), revealing a photon avalanche process under 1208 nm laser excitation, as well as GSA and ESA at other excitation wavelengths. The NaYF₄:2%Tm³⁺@NaYF₄:5%Er³⁺ NPs revealed the resultant emission properties, as the dopant ions were separated within core and shell phases. The NaYF₄:18%Yb³⁺,2%Tm³⁺@NaYF₄ and NaYF₄:18%Yb³⁺,2%Tm³⁺@NaYF₄:5%Er³⁺ samples showed the brightest emission, around 800 nm, under 975 nm excitation, though other laser wavelengths allowed for observation of luminescence, as well, especially in NPs with Er³⁺ in the outer shell, capable of UC under 1532 nm. The presented results highlight the unique and universal properties of lanthanide ions for designing luminescent NPs for a variety of potential applications, such as confocal microscopy.