Upconversion photoluminescence of Ho3+-Yb3+ doped barium titanate nanocrystallites: Optical tools for structural phase detection and temperature probing.

Authors have explored the photo-physical properties of Ho3+-Yb3+ doped BaTiO3 nanocrystals and proposed an intuitive method to probe temperature and crystal phase structure of the matrix. Structural phase change of doped crystals was analyzed in terms of their X-ray diffraction, and it was confirmed through second harmonic generation. We give insights on upconversion of energy of light-emission in Ho3+-Yb3+: BaTiO3 nanocrystals upon a 980 nm laser-light excitation and subsequently, the excited state dynamics were studied with the help of dependence of upconversion luminescence on excitation power and measuring-temperature. To understand the nature of occupancies of the Ho3+ ions at the Ti- and Ba-sites, we performed site-selective, time-resolved spectroscopic measurements at various crystal phases. Based on the lifetime analysis, it is inferred that the Ho3+ ions are present at two types of sites in barium titanate lattice. One of those is the 6-coordinated Ti-site of low symmetry, while the other one is the 12-coordinated Ba-site of higher symmetry. The upconversion emission of the nanocrystals are found to be temperature-sensitive (12 to 300 K), indicating possible use as a self-referenced temperature probe. An analysis of the temperature dependent emissions from 5F4 and 5S2 levels of Ho3+ ions, gives a maximum value of temperature sensitivity ~ 0.0095 K-1 at 12 K. Furthermore, we observe a sharp change in the luminescence intensity at ~180 K due to a ferroelectric phase change of the sample. The correlation of upconversion luminescence with the results of X-ray diffraction and second harmonic generation at different crystal phases implies that the frequency upconversion may be used as a probe of structural change of the lattice.

Demonstration of Temperature Dependent Energy Migration in Dual-Mode YVO4: Ho3+/Yb3+ Nanocrystals for Low Temperature Thermometry.

A dual mode rare-earth based vanadate material (YVO4: Ho3+/Yb3+), prepared through ethylene glycol assisted hydrothermal method, demonstrating both downconversion and upconversion, along with systematic investigation of the luminescence spectroscopy within 12-300 K is presented herein. The energy transfer processes have been explored via steady-state and time-resolved spectroscopic measurements and explained in terms of rate equation description and temporal evolution below room temperature. The maximum time for energy migration from host to rare earth (Ho3+) increases (0.157 µs to 0.514 µs) with the material's temperature decreasing from 300 K to 12 K. The mechanism responsible for variation of the transients' character is discussed through thermalization and non-radiative transitions in the system. More significantly, the temperature of the nanocrystals was determined using not only the thermally equilibrated radiative intra-4f transitions of Ho3+ but also the decay time and rise time of vanadate and Ho3+ energy levels. Our studies show that the material is highly suitable for temperature sensing below room temperature. The maximum relative sensor sensitivity using the rise time of Ho3+ energy level (5F4/5S2) is 1.35% K-1, which is the highest among the known sensitivities for luminescence based thermal probes.

Incorporation of Zn(2+) ions into BaTiO3:Er(3+)/Yb(3+) nanophosphor: an effective way to enhance upconversion, defect luminescence and temperature sensing.

Ferroelectric BaTiO3 became a multifunctional material via doping of lanthanide ions (0.3 mol% Er(3+)/3.0 mol% Yb(3+)) and subsequently upconversion luminescence was enhanced by incorporation of Zn(2+) ions. Upconversion luminescence of BaTiO3:Er(3+)/Yb(3+) perovskite nanophosphor has been studied using 800 and 980 nm laser excitations. The emission dynamics is studied with respect to its dependence on input power and external temperature including lifetime. Based on time-resolved spectroscopy, it is inferred that two types of Er(3+) sites are present in the barium titanate lattice. The first one is a short lived component (minor species) present at 6-coordinated Ti-sites of low symmetry while the second one is a long lived component (major species), present at 12-coordinated Ba-sites with high symmetry. The influence of the introduction of Zn(2+) ions on the lifetime of (4)S3/2 and (4)F9/2 levels of Er(3+) ions is also investigated. Enhanced temperature sensing performance (120 K to 505 K) of the material is observed using the fluorescence intensity ratio technique, employing the emission from the thermally coupled, (2)H11/2 and (4)S3/2 energy levels of Er(3+) ions. The defect luminescence of the material is also found to increase upon Zn-doping.