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Energy Transfer Networks Within Upconverting Nanoparticles Are Complex Systems With Collective, Robust, and History-Dependent Dynamics
摘要： Applications of photon upconverting nanoparticles (UCNPs) in biological imaging and solar energy conversion demand that their anti-Stokes luminescence be both tunable and efficient. Rational design of more efficient UCNPs requires an understanding of energy transfer (ET) between their lanthanide dopants – dynamics that are typically characterized by measuring luminescence lifetimes. Existing knowledge, however, cannot explain basic observations in lifetime experiments such as their dependence on excitation power, significantly limiting the generality and reliability of lifetime measurements. Here, we elucidate the origins of the ET dynamics and luminescence lifetimes of Yb3+,Er3+-codoped NaYF4 UCNPs using time-resolved luminescence and novel applications of rate equations and stochastic simulations. Experiments and calculations consistently show that, at high concentrations of Er3+, the luminescence lifetimes of UCNPs decrease as much as 6-fold when excitation power densities are increased over six orders of magnitude. Since power-dependent lifetimes cannot be explained by intrinsic relaxation rates of individual transitions, we analyze lifetime data by treating each UCNP as a complex ET network. We find that UCNP ET networks exhibit four distinguishing characteristics of complex systems: collectivity, nonlinear feedback, robustness, and history dependence. We conclude that power-dependent lifetimes are the consequence of thousands of minor relaxation pathways that act collectively to depopulate and repopulate Er3+ emitting levels. These ET pathways are dependent on past excitation power because they originate from excited donors and excited acceptors; however, each transition has an unexpectedly small impact on lifetimes due to negative feedback in the network. This robustness is determined by systematically 'knocking out,' or disabling, ET transitions in kinetic models. Our classification of UCNP ET networks as complex systems explains why UCNP luminescence lifetimes do not match the intrinsic lifetimes of emitting states. In the future, UCNP networks may be engineered to rival the complexity of biological networks that pattern features with unmatched precision.
关键词： complex systems,energy transfer,upconverting nanoparticles,lanthanide dopants,power dependence,luminescence lifetimes
更新于2025-09-19 17:15:36
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Reliability of rare-earth-doped infrared luminescent nanothermometers
摘要： The use of infrared-emitting rare-earth-doped luminescent nanoparticles as nanothermometers has attracted great attention during the last few years. The scientific community has identified rare-earth-doped luminescent nanoparticles as one of the most sensitive and versatile systems for contactless local temperature sensing in a great variety of fields, but especially in nanomedicine. Researchers are nowadays focused on the design and development of multifunctional nanothermometers with new spectral operation ranges, outstanding brightness, and enhanced sensitivities. However, no attention has been paid to the assessment of the actual reliability of the measurements provided by rare-earth-doped luminescent nanothermometers. In fact, it is assumed that they are ideal temperature sensors. Nevertheless, this is far from being true. In this work we demonstrate that the emission spectra of rare-earth-doped nanothermometers can be affected by numerous environmental and experimental factors. These include the numerical aperture of the optical elements used for their optical excitation and luminescence collection, the local concentration of nanothermometers, optical length variations, self-absorption of the luminescence by the nanothermometers themselves, and solvent optical absorption. This work concludes that rare-earth-doped luminescent nanothermometers are not as reliable as thought and, consequently, special care has to be taken when extracting temperature estimations from the variation of their emission spectra.
关键词： reliability,solvent absorption,self-absorption,excitation power dependence,infrared luminescent nanothermometers,rare-earth-doped
更新于2025-09-19 17:15:36
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Temperature and pressure induced Raman studies of C 60 oxide
摘要： We present temperature, laser power, and pressure dependent Raman spectral analysis of C60 oxide (C60O) thin films prepared by the photolysis method. The first order temperature, laser power, and pressure coefficients of the Raman frequencies are evaluated and are utilized for evaluating the thermal conductivity of C60O. Its thermal conductivity is found to be 0.7 W m-1 K-1 which is marginally higher than that of bulk C60. Raman frequencies corresponding to C–O and C–C bonds blue-shift with a decrease in temperature which is attributed to the thermal contraction of C60O molecules. The density functional measurements have been performed to optimize C60O structure. The contraction in the C–O bond length has been corroborated with the experimental Raman shifts at different temperatures and is used to evaluate the linear expansion coefficient of C60O. Pressure induced compression and polymerization of C60O clusters are also illustrated. This study highlights the interplay between thermal and mechanical transformations in the C60O cluster which may regulate its thermoelectric properties by tuning the intermolecular interactions.
关键词： pressure dependence,thermoelectric properties,Raman spectroscopy,thermal conductivity,C60 oxide,laser power dependence,temperature dependence
更新于2025-09-09 09:28:46