The influence of Ce3+ codoping on upconversion in nanocrystalline NaYF4:Yb3+,Tm3+

Abstract

Usually, to obtain multicolor upconversion in lanthanides, materials with different codopants, different size, chemical composition or compositional architecture are required. However, designing a material whose emission color can be tuned in-situ by an external stimulus, such as temperature, excitation pulse duration or photoexcitation density, is of great interest for many applications, but still remains a challenge. The possible solution for this issue can be achieved by intentional codoping the luminescent materials with optically active ions which can disturb or compete with other energy transfer processes, and in consequence lead to changes in relative emission intensity, thus the dominant emission color. Here we synthesized and investigated colloidal luminescent Yb3+ and Tm3+ doped NaYF4 nanoparticles which were codoped with optically active Ce3+ ions, whose relative emission intensity ratios between 1D2→3F4 (at 450 nm), 1G4→3H6 (at 475 nm), 1G4→3F4 (at 650 nm), and 3H4→3H6 (at 800 nm) were significantly dependent from external stimulus – namely temperature and/or excitation pulse length. Our results shows two fold increase in 450/800, 470/800 and 650/800 luminescence intensity bands ratios (LIR) only after incorporation of Ce3+ ions to the material, and even three-fold increase in those LIR after changing the excitation conditions (i.e. pulse width). Moreover, temperature dependent luminescence properties revealed relative sensitivity of 4%/K for the 450/800 and 470/800 bands ratio and almost 5.5%/K for the 650/800 band ratio close to 0 °C. By switching to physiological range of temperatures, the thermal sensitivity decreased to around 2%/K for the 450/800 and 470/800 bands ratio and to over 2.5%/K for 650/800 bands ratio, which should be considered as significant values and suitable for temperature sensing in practical applications. It is worth noting that the thermal sensitivity values can be further enhanced by applying different excitation pulse width. The proposed materials allows to tune its emissions as well as thermal properties by changing the dopant concentration or more importantly also in situ, through excitation scheme modifications.