Temperature (T) is probably the most fundamental parameter in all kinds of science. Respective sensors are widely used in daily life. Besides conventional thermometers, optical sensors are considered to be attractive alternatives for sensing and on-line monitoring of T. This Review article focuses on all kinds of luminescent probes and sensors for measurement of T, and summarizes the recent progress in their design and application formats. The introduction covers the importance of optical probes for T, the origin of their T-dependent spectra, and the various detection modes. This is followed by a survey on (a) molecular probes, (b) nanomaterials, and (c) bulk materials for sensing T. This section will be completed by a discussion of (d) polymeric matrices for immobilizing T-sensitive probes and (e) an overview of the various application formats of T-sensors. The review ends with a discussion on the prospects, challenges, and new directions in the design of optical T-sensitive probes and sensors.

Luminescent probes and sensors for temperature.

Non-invasive precise thermometers working at the nanoscale with high spatial resolution, where the conventional methods are ineffective, have emerged over the last couple of years as a very active field of research. This has been strongly stimulated by the numerous challenging requests arising from nanotechnology and biomedicine. This critical review offers a general overview of recent examples of luminescent and non-luminescent thermometers working at nanometric scale. Luminescent thermometers encompass organic dyes, QDs and Ln3+ions as thermal probes, as well as more complex thermometric systems formed by polymer and organic–inorganic hybrid matrices encapsulating these emitting centres. Non-luminescent thermometers comprise of scanning thermal microscopy, nanolithography thermometry, carbon nanotube thermometry and biomaterials thermometry. Emphasis has been put on ratiometric examples reporting spatial resolution lower than 1 micron, as, for instance, intracellular thermometers based on organic dyes, thermoresponsive polymers, mesoporous silica NPs, QDs, and Ln3+-based up-converting NPs and β-diketonate complexes. Finally, we discuss the challenges and opportunities in the development for highly sensitive ratiometric thermometers operating at the physiological temperature range with submicron spatial resolution.

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Thermometry at the nanoscale

Luminescent ratiometric thermometers combining high spatial and temporal resolution at the micro- and nanoscale, where the conventional methods are ineffective, have emerged over the last decade as an effervescent field of research, essentially motivated by their potential applications in nanotechnology, photonics, and biomedicine. Among the distinct luminescent thermal probes, lanthanide-based materials play a central role in the field due to their unique thermometric response and intriguing emission features (eg, high quantum yield, narrow bandwidth, long-lived emission, large Stokes shifts, and ligand-dependent luminescence sensitization). This chapter offers a general overview of recent examples of single- and dual-center Ln3 +-based thermometers, emphasizing those working at nanometric scale, being focused on how to quantify their performance accordingly to the relevant parameters: relative sensitivity, temperature uncertainty, spatial and temporal resolution, repeatability (or test–retest reliability), and reproducibility. The emission mechanisms supporting single- and dual-center emissions are reviewed, together with the advantages and limitations of each approach. Illustrative examples of the rich variety of systems designed and developed to sense temperature are provided and explored. Finally, we discuss the challenges and opportunities in the development of highly sensitive luminescent ratiometric thermometers that are currently facing the scientists in this exciting research field.

Lanthanides in Luminescent Thermometry

A single nanoplatform integrating laser-induced heat generation by gold nanoparticles and temperature sensing up to 2000 K via (Gd,Yb,Er)2 O3 nanorods is demonstrated, which presents considerable potential for nanoscale photonics and biomedicine. Blackbody emission is ascertained from the temperature increment with AuNP concentration, emission color coordinates as a function of the laser pump power, and Planck's law of blackbody radiation.

All-in-one optical heater-thermometer nanoplatform operative from 300 to 2000 k based on Er(3+) emission and blackbody radiation.

Dr. A. Benayas, Prof. F. Vetrone Institut National de la Recherche Scientiﬁ que Centre – Energie Materiaux et Telecommunications 1650, Boul. Lionel Boulet Varennes , QC J3X 1S2 , Canada E-mail: antonio.benayas@emt.inrs.ca B. del Rosal, A. Perez-Delgado, Dr. D. Jaque Fluorescence Imaging GroupDepartamento de Fisica de Materiales Facultad de Ciencias, Universidad Autonoma de Madrid Campus de Cantoblanco Madrid 28049 , Spain Dr. K. Santacruz-Gomez Departamento de Fisica, Universidad de Sonora Rosales y Blvd. Luis Encinas s/n CP 8300 , Hermosillo , Sonora , Mexico Dr. D. Jaque IRYCIS, Instituto Ramon y Cajal de Investigacion Sanitaria. Hospital Ramon y Cajal, 28034 Madrid, Spain Dr. G. A. Hirata Centro de Nanociencias y Nanotecnologia Universidad Nacional Autonoma de Mexico Ensenada , Baja California C.P. 22860 , Mexico

Nd:YAG Near-Infrared Luminescent Nanothermometers

It is shown that due to the inherent irreversible non-fluorescence to fluorescence transition feature of polydiacetylene (PDA) supramolecules that occurs in response to thermal perturbations, PDA vesicles embedded in a host polymer matrix function as nano/microscale temperature indicators. As a result, they are used to monitor temperature gradients on an integrated circuit chip and to uncover submicrometer size filamentary defects in a resistance random access memory (RRAM) device structure. This new methodology should find a wide applicability in carrying out temperature distribution analysis on semiconductor and micro-electromechanical system (MEMS) devices where the detection of local heat deviations of small-scale components is critical.

Thermofluorescent Conjugated Polymer Sensors for Nano- and Microscale Temperature Monitoring

A direct method for the generation of magnetically responsive conjugated polymer supramolecules is described. By immobilizing magnetite nanoparticles (MNP) on the surface of polydiacetylene (PDA) supramolecules, an inorganic/conjugated polymer hybrid system results that enables the incorporation of an important property (magnetism) to an attractive class of colorimetric PDA sensors. Benefits of this new system include: (1) ease of preparation, (2) variability in diacetylene labeling of MNPs, (3) diversity in conjugated PDA morphologies, (4) facile isolation process, and (5) immobilization of the PDA without altering the colorimetric (sensory) properties. It is demonstrated that PDA/MNP systems offer advantages in applications including film formation, separation, and sensing.

Magnetically Responsive Inorganic/Polydiacetylene Nanohybrids

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Thermofluorescent Conjugated Polymer Sensors for Nano- and Microscale Temperature Monitoring

Magnetically Responsive Inorganic/Polydiacetylene Nanohybrids