Near‐Infrared Ratiometric Luminescent Thermometer Based on a New Lanthanide Silicate

Ananias, Duarte; Paz, Filipe A. Almeida; Carlos, Luı́s D.; Rocha, João

doi:10.1002/chem.201802219

Cited by 31 publications

(10 citation statements)

References 54 publications

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“…The connected relative sensitivities, S r ( T ), as defined by in the case of a Boltzmann thermometer that varies between S r (30 K) = 11.6% K −1 and S r (51 K) = 3.98% K −1 in this optimum range, which is clearly above the usually desired threshold of S r = 1% K −1 in practice 23 . In fact, the relative sensitivity at 30 K is the highest reported value for luminescent cryothermometers at that particular temperature thus far 50 , 67 , 68 , 79 , 80 . It is important to note, however, that it is both the balance between reliably detectable luminescence signals and relative sensitivity that determine the overall precision of a luminescent thermometer (see also below) 55 , 81 .…”

Section: Resultsmentioning

confidence: 78%

One ion to catch them all: Targeted high-precision Boltzmann thermometry over a wide temperature range with Gd3+

Zhang

et al. 2021

Light Sci Appl

102

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Ratiometric luminescence thermometry with trivalent lanthanide ions and their 4fn energy levels is an emerging technique for non-invasive remote temperature sensing with high spatial and temporal resolution. Conventional ratiometric luminescence thermometry often relies on thermal coupling between two closely lying energy levels governed by Boltzmann’s law. Despite its simplicity, Boltzmann thermometry with two excited levels allows precise temperature sensing, but only within a limited temperature range. While low temperatures slow down the nonradiative transitions required to generate a measurable population in the higher excitation level, temperatures that are too high favour equalized populations of the two excited levels, at the expense of low relative thermal sensitivity. In this work, we extend the concept of Boltzmann thermometry to more than two excited levels and provide quantitative guidelines that link the choice of energy gaps between multiple excited states to the performance in different temperature windows. By this approach, it is possible to retain the high relative sensitivity and precision of the temperature measurement over a wide temperature range within the same system. We demonstrate this concept using YAl3(BO3)4 (YAB):Pr3+, Gd3+ with an excited 6PJ crystal field and spin-orbit split levels of Gd3+ in the UV range to avoid a thermal black body background even at the highest temperatures. This phosphor is easily excitable with inexpensive and powerful blue LEDs at 450 nm. Zero-background luminescence thermometry is realized by using blue-to-UV energy transfer upconversion with the Pr3+−Gd3+ couple upon excitation in the visible range. This method allows us to cover a temperature window between 30 and 800 K.

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Section: Resultsmentioning

confidence: 78%

One ion to catch them all: Targeted high-precision Boltzmann thermometry over a wide temperature range with Gd3+

Zhang

et al. 2021

Light Sci Appl

102

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“…[87][88][89][90][91] If doped into thermally stable inorganic nano-or microcrystalline hosts, lanthanides thus found many promising applications such as Pr 3+ , [19,[92][93][94][95] Nd 3+ (often sensitized with Yb 3+ ) [33, or Tm 3+ [122][123][124] in the field of room temperature sensing and thermal bioimaging. Er 3+ and Yb 3+ is the traditional lanthanide couple for upconversion-based in vivo imaging, [125][126][127][128][129][130][131][132][133] or in situ temperature monitoring of catalytic reactions or flow reactions in microfluidic devices. [85,86,[134][135][136][137][138] Recently reported creative alternatives of the use of this upconversion couple were vacuum sensing [139] or photothermal conversion.…”

Section: Introductionmentioning

confidence: 99%

A Theoretical Framework for Ratiometric Single Ion Luminescent Thermometers—Thermodynamic and Kinetic Guidelines for Optimized Performance

Suta

Meijerink

2020

Advcd Theory and Sims

198

191

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Luminescence (nano)thermometry is an increasingly important field for remote temperature sensing with high spatial resolution. Most typically, ratiometric sensing of the luminescence emission intensities of two thermally coupled emissive states based on a Boltzmann equilibrium is used to detect the local temperature. Dependent on the temperature range and preferred spectral window, various choices for potential candidates appear possible. Despite extensive experimental research in the field, a universal theory covering the basics of luminescence thermometry is virtually nonexistent. In this manuscript, a general theoretical framework of single ion luminescent thermometers is presented that offers simple, user-friendly guidelines for both the choice of an appropriate emitter and respective embedding host material for optimum temperature sensing. The results show that the optimum performance (thermal response and sensitivity) around T 0 is realized for an energy gap ∆E 21 between thermally coupled levels between 2k B T 0 and 3.41k B T 0. Analysis of the temperature-dependent excited state kinetics shows that host lattices in which ∆E 21 can be bridged by one or two phonons are preferred over hosts in which higher order phonon processes are required. Such a framework is relevant for both a fundamental understanding of luminescent thermometers but also the targeted design of novel and superior luminescent (nano)thermometers.

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“…Nevertheless, to evaluate the performance of the luminescence thermometer, the relative sensitivity is an important figure of merit reported in several materials ( Ananias et al . , 2018 ; Runowski et al .…”

Section: Resultsmentioning

confidence: 99%

Single Er3+, Yb3+: KGd3F10 Nanoparticles for Nanothermometry

et al. 2021

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Among several optical non-contact thermometry methods, luminescence thermometry is the most versatile approach. Lanthanide-based luminescence nanothermometers may exploit not only downshifting, but also upconversion (UC) mechanisms. UC-based nanothermometers are interesting for biological applications: they efficiently convert near-infrared radiation to visible light, allowing local temperatures to be determined through spectroscopic investigation. Here, we have synthesized highly crystalline Er3+, Yb3+ co-doped upconverting KGd3F10 nanoparticles (NPs) by the EDTA-assisted hydrothermal method. We characterized the structure and morphology of the obtained NPs by transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and dynamic light scattering. Nonlinear spectroscopic studies with the Er3+, Yb3+: KGd3F10 powder showed intense green and red emissions under excitation at 980 and 1,550 nm. Two- and three-photon processes were attributed to the UC mechanisms under excitation at 980 and 1,550 nm. Strong NIR emission centered at 1,530 nm occurred under low 980-nm power densities. Single NPs presented strong green and red emissions under continuous wave excitation at 975.5 nm, so we evaluated their use as primary nanothermometers by employing the Luminescence Intensity Ratio technique. We determined the temperature felt by the dried NPs by integrating the intensity ratio between the thermally coupled 2H11/2→4I15/2 and 4S3/2→4I15/2 levels of Er3+ ions in the colloidal phase and at the single NP level. The best thermal sensitivity of a single Er3+, Yb3+: KGd3F10 NP was 1.17% at the single NP level for the dry state at 300 K, indicating potential application of this material as accurate nanothermometer in the thermal range of biological interest. To the best of our knowledge, this is the first promising thermometry based on single KGd3F10 particles, with potential use as biomarkers in the NIR-II region.

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Near‐Infrared Ratiometric Luminescent Thermometer Based on a New Lanthanide Silicate

Cited by 31 publications

References 54 publications

One ion to catch them all: Targeted high-precision Boltzmann thermometry over a wide temperature range with Gd3+

One ion to catch them all: Targeted high-precision Boltzmann thermometry over a wide temperature range with Gd3+

A Theoretical Framework for Ratiometric Single Ion Luminescent Thermometers—Thermodynamic and Kinetic Guidelines for Optimized Performance

Single Er3+, Yb3+: KGd3F10 Nanoparticles for Nanothermometry

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