Preparation of NaYF4:Yb3+,Tm3+@NaGdF4:Ce3+,Eu3+ double-jacket microtubes for dual-mode fluorescent anti-counterfeiting

Abstract

Abstract Novel hydrophilic NaYF4:Yb3+,Tm3+@NaGdF4:Ce3+,Eu3+ double-jacket microtubes (DJMTs) with upconversion/ downconversion dual-mode luminescence were designed and prepared through epitaxial growth of NaGdF4:Ce3+, Eu3+ shell onto the NaYF4:Yb3+,Tm3+ microtube via poly(acrylic acid) (PAA) mediated hydrothermal method. It is demonstrated that PAA ligand played an important role in guiding the direct growth of NaGdF4:Ce3+,Eu3+ shell onto the surface of NaYF4:Yb3+,Tm3+ parent microtubes. The growth of NaGdF4:Ce3+,Eu3+ shell experienced a crystal phase transition from β-NaGdF4 and β-NaYF4 mixture to β-NaYF4@NaGdF4 composite crystal, and morphology evolution from mixture of β-NaGdF4:Ce3+,Eu3+ nanorods and β-NaYF4:Yb3+,Tm3+ microtubes to NaYF4:Yb3+,Tm3+@NaGdF4: Ce3+,Eu3+ DJMTs. The formation mechanism of DJMTs was the dissolution−renucleation of β-NaGdF4:Ce3+,Eu3+ nanorods and the growth of β-NaGdF4:Ce3+,Eu3+ shell via the classical Ostwald ripening mechanism. The as-prepared DJMTs could exhibit blue upconversion and red downconversion luminescence, which was further made into environmentally benign luminescent inks for creating highly secured and fluorescent-based anti-counterfeiting patterns via inkjet printing.