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A Luminescent Molecular Thermometer for Long-Term Absolute Temperature Measurements at the Nanoscale.pdf

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A Luminescent Molecular Thermometer for Long-Term Absolute Temperature Measurements at the Nanoscale

www.advmat.de www.MaterialsV C O M M A Luminescent Molecular Thermometer for Long-Term Absolute Temperature Measurements at the Nanoscale U N IC A TI By Carlos D. S. Brites , Patricia P. Lima , Nuno J. O. Silva , Angel Millán , Vitor S. Amaral , Fernando Palacio , * and Luís D. Carlos * O N Temperature is a fundamental thermodynamic variable, the measurement of which is crucial in countless scientifi c investi- gations and technological developments, accounting at present for 75%–80% of the sensor market throughout the world. [ 1 ] Traditional liquid-fi lled and bimetallic thermometers, thermo- couples, pyrometers, and thermistors are generally not suit- able for temperature measurements at scales below 10 μ m. This intrinsic limitation has encouraged the development of new non-contact accurate thermometers with micrometric and nanometric precision, a challenging research topic increasingly hankered for. [ 2–9 ] Current developments [ 4 ] of thermometers operating below a few micrometers and with high spatial resolution include: Ga-fi lled carbon/MnO nanotubes, [ 2 ] temperature-dependent conformation modifi cations of molecular spring superstruc- tures, [ 3 ] Raman [ 10 ] and infrared [ 11 ] spectroscopic probing, scan- ning thermal microscopy probes, [ 6 ] and luminescence-based measurements. [ 5–9 , 12–29 ] Nanotube-based systems require a transmission electron microscope for the read-out and calibration, an evident limita- tion for practical applications. Infrared observation is restricted by diffraction resolution and other spectroscopic methods (such as Raman), and scanning microscopy systems have a read-out rate limited by material surface conditions and probe motion (typically 30 ms per pixel, [ 29 ] making real-time temperature mapping unfeasible). By contrast, the thermal dependence of phosphor (organic dyes or trivalent lanthanides, Ln 3 + ) lumines- cence is a noninvasive and accurate alternative technique that w