The role of Li+ in the upconversion emission enhancement of (YYbEr)2O3 nanoparticles

The mechanism of upconversion enhancement for Li+-doped materials is still contentious. Attempting to settle the debate, here the upconversion emission enhancement of (Y0.97-xYb0.02Er0.01Lix)2O3, x = 0.000-0.123, nanoparticles is studied. Li+ incorporation in the Y2O3 host lattice is achieved via co-precipitation and solid-state reaction routes. In contrast to numerous reports, elemental analysis reveals that the former method does not afford Li+-bearing nanoparticles. The solid-state reaction route accomplishes an effective Li+ doping, as witnessed by inductively coupled plasma atomic emission spectroscopy and X-ray photoelectron spectroscopy (XPS). Transmission electron microscopy and powder X-ray diffraction showed an increase in nanoparticle size with increasing Li+ concentration. Rietveld refinement of powder X-ray diffraction data shows that the cubic lattice parameter decreases with increasing Li+ content. The emission quantum yield increases tenfold with increasing Li+ content up to x = 0.123, reaching a maximal value of 0.04% at x = 0.031. XPS and infrared spectroscopy show that the carbonate groups increase with increasing Li+ content, thus not supporting the prevailing view that the upconversion luminescence enhancement observed upon Li+ nanoparticle's doping is due to the decrease of the number of quenching carbonate groups present. Rather, the particle size increment and the decrease in the lattice parameter of the host crystals are shown to be the prime sources of quantum yield enhancement.publishe

Energy-transfer from Gd(III) to Tb(III) in (Gd,Yb,Tb)PO4 nanocrystals

The photoluminescence properties of (Gd,Yb,Tb)PO4 nanocrystals synthesized via a hydrothermal route at 150 degrees C are reported. Energy-transfer from Gd3+ to Tb3+ is witnessed by the detailed analyses of excited-state lifetimes, emission quantum yields, and emission and excitation spectra at room temperature, for Tb3+ concentrations ranging from 0.5 to 5.0 mol%. Absolute-emission quantum yields up to 42% are obtained by exciting within the (6I)7/2-17/2 (Gd3+) manifold at 272 nm. The room temperature emission spectrum is dominated by the D-5(4) -> F-7(5) (Tb3+) transition at 543 nm, with a long decay-time (3.95-6.25 ms) and exhibiting a rise-time component. The D-5(3) -> F-7(6) (Tb3+) rise-time (0.078 ms) and the P-6(7/ 2) -> S-8(7/2) (Gd3+) decay-time (0.103 ms) are of the same order, supporting the Gd3+ to Tb3+ energy-transfer process. A remarkably longer lifetime of 2.29 ms was measured at 11 K for the P-6(7/2) -> S-8(7/2) (Gd3+) emission upon excitation at 272 nm, while the emission spectrum at 11 K is dominated by the P-6(7/2) -> S-8(7/2) transition line, showing that the Gd3+ to Tb3+ energy-transfer process is mainly phonon-assisted with an efficiency of similar to 95% at room temperature. The Gd3+ to Tb3+ energy transfer is governed by the exchange mechanism with rates between 10(2) and 10(3) s(-1), depending on the energy mismatch conditions between the (6I)(7/2) and P-6(7/2) levels of Gd3+ and the Tb3+ I-5(7), F-5(2,3) and H-5(5,6,7) manifolds and the radial overlap integral values

Nanoplatforms for Plasmon-Induced Heating and Thermometry

Plasmonic nanostructures concentrate light and heat within a small volume at the nanoscale, offering potential applications in nanotechnology and biomedicine (e.g., hyperthermia). However, the precise quantification of the actual temperature rise in the vicinity of such nanosystems poses considerable challenges. Here, we present a new heater-thermometer nanoplatform capable of measuring the plasmon-induced local temperature increase of Au nanorods via the ratiometric upconversion of (Gd, Yb, Er)(2)O-3 nanothermometers upon 980 nm laser excitation (up to 102.0 Wcm(-2)). The local temperature rise, 302-548 K (maximum temperature sensitivity 1.22% K-1, uncertainty 0.32K and repeatability > 99%), is assessed using Boltzmann's distribution of the Er3+ (2)H1(11/2) -> I-4(15/2)/S-4(3/2) -> I-4(15/2) intensity ratio. The nanoplatforms are biocompatible with MG-63 and A549 cells and were mapped within the former using hyperspectral imaging, opening up an avenue to monitor the cellular uptake of Ln(3+)-based nanoplatforms

Boosting the sensitivity of Nd3+-based luminescent nanothermometers

Luminescence thermal sensing and deep-tissue imaging using nanomaterials operating within the first biological window (ca. 700-980 nm) are of great interest, prompted by the ever-growing demands in the fields of nanotechnology and nanomedicine. Here, we show that (Gd1-xNdx)(2)O-3 (x = 0.009, 0.024 and 0.049) nanorods exhibit one of the highest thermal sensitivity and temperature uncertainty reported so far (1.75 +/- 0.04% K-1 and 0.14 +/- 0.05 K, respectively) for a nanothermometer operating in the first transparent near infrared window at temperatures in the physiological range. This sensitivity value is achieved using a common R928 photomultiplier tube that allows defining the thermometric parameter as the integrated intensity ratio between the F-4(5/2) -> I-4(9/2) and F-4(3/2) -> I-4(9/2) transitions (with an energy difference between the barycentres of the two transitions > 1000 cm(-1)). Moreover, the measured sensitivity is one order of magnitude higher than the values reported so far for Nd3+-based nanothermometers enlarging, therefore, the potential of using Nd3+ ions in luminescence thermal sensing and deep-tissue imaging

Upconverting Nanoparticles Working As Primary Thermometers In Different Media

In the past decade, noninvasive luminescent thermometry has become popular due to the limitations of traditional contact thermometers to operate at scales below 100 μm, as required by current demands in disparate areas. Generally, the calibration procedure requires an independent measurement of the temperature to convert the thermometric parameter (usually an intensity ratio) to temperature. A new calibration procedure is necessary whenever the thermometer operates in a different medium. However, recording multiple calibrations is a time-consuming task, and not always possible to perform, e.g., in living cells and in electronic devices. Typically, a unique calibration relation is assumed to be valid, independent of the medium, which is a bottleneck of the secondary luminescent thermometers developed up to now. Here we report a straightforward method to predict the temperature calibration curve of any upconverting thermometer based on two thermally coupled electronic levels independently of the medium, demonstrating that these systems are intrinsically primary thermometers. SrF₂:Yb/Er powder and water suspended nanoparticles were used as an illustrative example

Instantaneous ballistic velocity of suspended Brownian nanocrystals measured by upconversion nanothermometry

Brownian motion is one of the most fascinating phenomena in nature(1,2). Its conceptual implications have a profound impact in almost every field of science and even economics, from dissipative processes in thermodynamic systems(3,4), gene therapy in biomedical research(5), artificial motors(6) and galaxy formation(7) to the behaviour of stock prices(8). However, despite extensive experimental investigations, the basic microscopic knowledge of prototypical systems such as colloidal particles in a fluid is still far from being complete. This is particularly the case for the measurement of the particles' instantaneous velocities, elusive due to the rapid random movements on extremely short timescales(9). Here, we report the measurement of the instantaneous ballistic velocity of Brownian nanocrystals suspended in both aqueous and organic solvents. To achieve this, we develop a technique based on upconversion nanothermometry. We find that the population of excited electronic states in NaYF4: Yb/Er nanocrystals at thermal equilibrium can be used for temperature mapping of the nanofluid with great thermal sensitivity (1.15% K-1 at 296 K) and a high spatial resolution (< 1 mu m). A distinct correlation between the heat flux in the nanofluid and the temporal evolution of Er3+ emission allows us to measure the instantaneous velocity of nanocrystals with different sizes and shapes

3D sub-cellular localization of upconverting nanoparticles through hyperspectral microscopy

Hyperspectral microscopy is an intriguing technique combining spectroscopy with optical microscopy that can be used to simultaneously obtain spectral and spatial information. The relevance of hyperspectral imaging in biomedical applications such as the monitoring of bioimaging agents, the identification of pathogens and cancerous cells, and the cellular uptake of nanoparticles has emerged recently, due to recent advances in optical reconstruction. The location and tracking of particles within the cell structure have been analyzed by 2D hyperspectral imaging of non-fluorescence objects, being examples of 3D localization uncommon. Here, we report the synthesis of Yb3+/Er3+-codoped Gd2O3 nanoparticles, their structural and luminescence characterization, and their biocompatibility assessments in Human melanoma (MNT-1 and A375) cell lines. The internalization of the particles by MNT-1 cells and their 3D localization in a fixed configuration are addressed through 2D optical images acquired in different planes along with the cell culture depth. 2D hyperspectral imaging is used to unequivocally identify the nuclei and the nanoparticles. The results indicate that the particles are distributed in distinct planes deep in the cell volume in the cytoplasmic and perinuclear regions. Furthermore, the emission signature of the nanoparticles enabled the determination of the intracellular temperaturepublishe