Near-infrared long persistent luminescence of Er<sup>3+</sup> in garnet for the third bio-imaging window

Xu, Jian; Murata, Daisuke; Ueda, Jumpei; Tanabe, Setsuhisa

doi:10.1039/c6tc04027f

Cited by 91 publications

(56 citation statements)

References 52 publications

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“…Applications of rare earth-doped inorganic materials are manifold, ranging from solid state lighting to scintillators, lasers, biomedical applications, multiphoton processes, temperature sensing, quantum information technology and many more. [1][2][3][4][5][6][7][8][9][10][11] Especially the 4f n-1 5d-4f n transitions of Eu 2+ (n = 7) and Ce 3+ (n = 1) are of great importance for phosphors used in phosphor-converted light-emitting diodes (pc-LEDs). 1,4,12,13 They usually show high emission intensities and also a strong dependence of the emission energy on the host material.…”

Section: Introductionmentioning

confidence: 99%

One Ion, Many Facets: Efficient, Structurally and Thermally Sensitive Luminescence of Eu²⁺ in Binary and Ternary Strontium Borohydride Chlorides

et al. 2019

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The Eu 2+ -doped mixed alkaline metal strontium borohydride chlorides ASr(BH4)3-xClx (A = K, Rb, Cs) and Eu 2+ -doped strontium borohydride chloride Sr(BH4)2-xClx have been prepared by mechanochemical synthesis. Intense blue photoluminescence for Sr(BH4)2-xClx (λem= 457 nm) and cyan photoluminescence for the perovskite-type mixed alkaline metal strontium borohydride chlorides ASr(BH4)3-xClx (A = K, Rb, Cs) (λem = 490 nm) is already observable after short milling times. Temperature dependent luminescence measurements reveal an appreciable blue shift with increasing temperature for all ASr(BH4)3-xClx (A = K, Rb, Cs) until 500 K. This extremely large shift, caused by structural relaxation, as well as the vibrationally induced emission band broadening can serve as a sensitive response signal for temperature sensing, and this unique behavior has, to the best of our knowledge, not been reported in any Eu 2+ doped phosphor so far. Additionally, bright luminescence, high quantum efficiencies, and very low thermal quenching of these Eu 2+ -doped borohydrides show that such host materials could serve in solid state lighting applications. xClx:Eu 2+ (A = K, Rb, Cs) for the first time. All discussed ternary compounds show efficient cyan emission at room temperature as well as a strongly temperature-dependent shift of the emission energies. This unusually strong response of the luminescence properties of Eu 2+ with Chemistry of Materials 2019, 31, 8957-8968 https://doi.org/10.1021/acs.chemmater.9b03048regard to temperature changes may be interesting for potential applications in the field of thermometry. Experimental sectionSynthesis. Due to moisture and air sensitivity all compounds were handled in an argon-filled glove box. The mixed metal borohydrides ASr(BH4)3-xClx:Eu 2+ (A = K, Rb, Cs) were prepared via mechanochemical reaction of LiBH4 (Alfa Aesar, 95%), SrCl2 (Alfa Aesar, 99.995%), the corresponding alkaline borohydrides (KBH4, Alfa Aesar 98%; RbBH4 and CsBH4 prepared from Rb or Cs metal and NaBH4 in ethanol according to the procedure described in Ref 34) as well as EuH2 (2 mol% doping; synthesized via hydrogenation of europium metal in an autoclave made from hydrogen-resistant Böhler L718 alloy) in a Fritsch Pulverisette Premium Line 7 in a ZrO2 bowl with an overpressure valve. Sr(BH4)2-xClx:Eu 2+ was prepared via mechanochemical reaction of stoichiometric amounts of SrCl2, LiBH4 and 2 mol% EuH2. 10 ZrO2 balls with a diameter of 10 mm are used together with approximately 0.3 g of reactants. Caution! Overpressure may build up during milling via decomposition of the borohydrides. Reactants were milled during 19 cycles with 2 minutes of milling at 600 rpm followed by 3 minutes pauses to prevent heating of the samples. To increase crystallinity, the samples were annealed at 200 °C in fused silica ampoules for 2 days. Powder x-ray diffraction (XRD). For powder XRD analysis, a STOE STADI P diffractometer (Cu-Kα1 radiation, λ = 1.54051 Å (determined from a silicon standard)), Ge-(111)monochromator) including a DECTRIS Mythen...

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Section: Introductionmentioning

confidence: 99%

One Ion, Many Facets: Efficient, Structurally and Thermally Sensitive Luminescence of Eu²⁺ in Binary and Ternary Strontium Borohydride Chlorides

et al. 2019

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“…In order to avoid this limitation, one would have to shift their operation spectral range from the visible to one of the so‐called biological windows (BWs), where both tissue absorption and scattering are minimized . There are, traditionally, three biological optical transparency windows (BW‐I: 650–950 nm, BW‐II: 1000–1350 nm, BW‐III: 1500–1800 nm), each of them contributing in a different manner to deep tissue imaging prospects . In terms of imaging, the BW‐I has the inconvenience of signal interference by tissue autofluorescence, nevertheless its remarkable tissue penetration properties are commonly exploited for effective near infrared (NIR) laser excitation .…”

Section: Introductionmentioning

confidence: 99%

In Vivo Subcutaneous Thermal Video Recording by Supersensitive Infrared Nanothermometers

Ximendes

Rocha

Sales

et al. 2017

Adv Funct Materials

170

119

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Some of the old and unrealizable dreams of biomedicine have become possible thanks to the appearance of novel advanced materials such as luminescent nanothermometers, nanoparticles capable of providing a contactless thermal reading through their light emission properties. Luminescent nanothermometers have already been demonstrated to be capable of in vivo subcutaneous punctual thermal reading but their real application as diagnosis tools still requires demonstrating their actual capacity for the acquisition of in vivo, time-resolved subcutaneous thermal images. The transfer from 1D to 2D subcutaneous thermal sensing is blocked in the last years mainly due to the lack of high sensitivity luminescent nanothermometers operating in the infrared biological windows. This work demonstrates how core/shell engineering, in combination with selective rare earth doping, can be used to develop supersensitive infrared luminescent nanothermometers. Erbium, thulium, and ytterbium core-shell LaF 3 nanoparticles, operating within the biological windows, provide thermal sensitivities as large as 5% °C −1 . This "record" sensitivity has allowed for the final acquisition of subcutaneous thermal videos of a living animal. Subsequent analysis of thermal videos allows for an unequivocal determination of intrinsic properties of subcutaneous tissues, opening the venue to the development of novel thermal imaging-based diagnosis tools.

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“…Near infrared (NIR) light (700–1800 nm) is translucent to biological tissues due to substantially reduced light scattering and absorption, thus entailing accurate luminescence readout in deep tissues. This spectral range is known to be classified into three “optical biological windows”: the first window (NIR‐I: 700–900 nm), the second window (NIR‐II: 1000–1350 nm), and the third window (NIR‐III: 1500–1870 nm) . The tissue‐penetrating ability promises the use of NIR LIR thermometers for biological uses.…”

Section: Introductionmentioning

confidence: 99%

NIR‐II/III Luminescence Ratiometric Nanothermometry with Phonon‐Tuned Sensitivity

Jia

et al. 2020

Advanced Optical Materials

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Luminescence nanothermometers are promising for noninvasive, high resolution thermographics ranging from aeronautics to biomedicine. Yet, limited success has been met in the NIR‐II/III biological windows, which allow temperature evaluation in deep tissues. Herein, a new type of phonon‐based ratiometric thermometry is described that utilizes the luminescence intensity ratio (LIR) between holmium (Ho3+) emission at ≈1190 nm (NIR‐II) and erbium (Er3+) emission at ≈1550 nm (NIR‐III) from a set of oxide nanoparticles of varying host lattices. It is shown that multi‐phonon relaxation in Er3+ ions and phonon‐assisted transfer process in Ho3+ ions play a significant role in LIR determination through channeling the harvested excitation energy to the corresponding emitting states. As a result, temperature sensitivity can be tuned by the dominant phonon energy of host lattice, thus endowing aqueous yttrium oxide (Y2O3, 376 cm−1) nanoparticles to have a relative temperature sensitivity of 1.01% K−1 and absolute temperature sensitivity of 0.0127 K−1 at 65 °C in a physiological temperature range (25–65 °C). And their temperature sensing for biological tissues is further explored and the influence of water and chicken breast on thermometry is discussed. This work constitutes a solid step forward to build sensitive NIR‐II/III nanothermometers for biological applications.

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Near-infrared long persistent luminescence of Er³⁺ in garnet for the third bio-imaging window

Abstract: ).We also show the first PersL imaging by a commercial InGaAs camera monitoring Er 3+ emission indicating that this material can be a promising candidate for in vivo bio-imaging in the NIR-III window.

Cited by 91 publications

References 52 publications

One Ion, Many Facets: Efficient, Structurally and Thermally Sensitive Luminescence of Eu²⁺ in Binary and Ternary Strontium Borohydride Chlorides

One Ion, Many Facets: Efficient, Structurally and Thermally Sensitive Luminescence of Eu²⁺ in Binary and Ternary Strontium Borohydride Chlorides

In Vivo Subcutaneous Thermal Video Recording by Supersensitive Infrared Nanothermometers

NIR‐II/III Luminescence Ratiometric Nanothermometry with Phonon‐Tuned Sensitivity

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Near-infrared long persistent luminescence of Er3+ in garnet for the third bio-imaging window

Abstract: ).We also show the first PersL imaging by a commercial InGaAs camera monitoring Er 3+ emission indicating that this material can be a promising candidate for in vivo bio-imaging in the NIR-III window.

Cited by 91 publications

References 52 publications

One Ion, Many Facets: Efficient, Structurally and Thermally Sensitive Luminescence of Eu2+ in Binary and Ternary Strontium Borohydride Chlorides

One Ion, Many Facets: Efficient, Structurally and Thermally Sensitive Luminescence of Eu2+ in Binary and Ternary Strontium Borohydride Chlorides

In Vivo Subcutaneous Thermal Video Recording by Supersensitive Infrared Nanothermometers

NIR‐II/III Luminescence Ratiometric Nanothermometry with Phonon‐Tuned Sensitivity

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Product

Resources

About

Near-infrared long persistent luminescence of Er³⁺ in garnet for the third bio-imaging window

One Ion, Many Facets: Efficient, Structurally and Thermally Sensitive Luminescence of Eu²⁺ in Binary and Ternary Strontium Borohydride Chlorides

One Ion, Many Facets: Efficient, Structurally and Thermally Sensitive Luminescence of Eu²⁺ in Binary and Ternary Strontium Borohydride Chlorides