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A special issue of Nanomaterials (ISSN 2079-4991).

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 17766

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Special Issue Editor

Dr. Łukasz Marciniak

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Guest Editor

Institute of Low Temperature and Structure Research of the Polish Academy of Sciences, Wroclaw, Poland
Interests: nanomaterials; luminescence; luminescent thermometry; multifunctional nanoparticles; up-conversion; light-to-heat conversion; luminescent imaging

Special Issue Information

Dear Colleagues,

Rare-earth-doped inorganic phosphors have been an exciting subject of research for decades due to their unique and fascinating luminescent properties, such as a strong emission intensity with sharp emission lines and long luminescent lifetimes. Their wide range of applications, including lighting, displays, scintillators, solid-state lasers, and optical storage, confirms their great importance. Doping lanthanide ions into nanoparticles not only extends the list of potential applications of rare-earth-doped phosphors but enables, among other things, the development of diagnostic and theranostic tools with unprecedented functionality. An appropriate composition, stoichiometry, and architecture of such nanoparticles will allow for the creation of multifunctional materials that combine optical temperature, pressure, and pH sensing with luminescence imaging and light-to-heat conversion. Although unparalleled and impressive, their capabilities have yet to be fully explored and understood.

To respond to the expectations of our readers and provide a picture of recent progress in the field of lanthanide nanocrystalline phosphors, we have established a Special Issue of Nanomaterials entitled “Luminescent Rare-Earth-Based Nanomaterials”.

Dr. Łukasz Marciniak
Guest Editor

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Keywords

luminescence
lanthanides
rare earth
optical properties
down shifting
down conversion
up conversion
luminescent thermometry
bioimaging
all optical sensors
light-to-heat convertors.

Published Papers (5 papers)

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Research

9 pages, 1813 KiB

Open AccessCommunication

Growth of Homogeneous Luminescent Silicon–Terbium Nanowires by One-Step Electrodeposition in Ionic Liquids

by Shibin Thomas, Jeremy Mallet, Bijal K. Bahuleyan and Michael Molinari

Nanomaterials 2020, 10(12), 2390; https://0-doi-org.brum.beds.ac.uk/10.3390/nano10122390 - 30 Nov 2020

Cited by 7 | Viewed by 1642

Abstract

An electrodeposition method for the growth of homogeneous silicon–terbium nanowires (NWs) with green light emission is described. The method involves template-assisted electrochemical co-deposition of Si/Tb NWs with 90-nm diameter from an electrolyte bath containing Si and Tb precursors in an ionic liquid (IL). This method of deposition is advantageous over other conventional techniques as it is relatively simple and cost-effective and avoids harsh deposition conditions. The deposited NWs are of uniform dimensions with homogeneous composition incorporating 10% of Tb and exhibit intense room temperature (RT) luminescence in the visible range due to Tb emission. These results were confirmed by combining classical characterization such as scanning electron microscopy (SEM) and photoluminescence (PL) performed on an assembly of NWs with spatially resolved experiments such as transmission electron microscopy (TEM) and cathodoluminescence (CL). This electrodeposition method provides an alternative and extremely simple approach for depositing silicon-rare earth nanostructures for optical and sensing applications. Full article

(This article belongs to the Special Issue Luminescent Rare-Earth-Based Nanomaterials)

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10 pages, 2319 KiB

Open AccessArticle

Comparison of Three Ratiometric Temperature Readings from the Er³⁺ Upconversion Emission

by Aleksandar Ćirić, Jelena Aleksić, Tanja Barudžija, Željka Antić, Vesna Đorđević, Mina Medić, Jovana Periša, Ivana Zeković, Miodrag Mitrić and Miroslav D. Dramićanin

Nanomaterials 2020, 10(4), 627; https://0-doi-org.brum.beds.ac.uk/10.3390/nano10040627 - 28 Mar 2020

Cited by 42 | Viewed by 3109

Abstract

The emission of Er³⁺ provides three combinations of emission bands suitable for ratiometric luminescence thermometry. Two combinations utilize ratios of visible emissions (²H_11/2→⁴I_15/2 at 523 nm/ ⁴S_3/2→⁴I_15/2 at 542 nm and ⁴F_7/2→⁴I_15/2 at 485 nm/ ⁴S_3/2→⁴I_15/2 at 545 nm), while emissions from the third combination are located in near-infrared, e.g., in the first biological window (²H_11/2→⁴I_13/2 at 793 nm/ ⁴S_3/2→⁴I_13/2 at 840 nm). Herein, we aimed to compare thermometric performances of these three different ratiometric readouts on account of their relative sensitivities, resolutions, and repeatability of measurements. For this aim, we prepared Yb³⁺,Er³⁺:YF₃ nanopowders by oxide fluorination. The structure of the materials was confirmed by X-ray diffraction analysis and particle morphology was evaluated from FE-SEM measurements. Upconversion emission spectra were measured over the 293–473 K range upon excitation by 980 nm radiation. The obtained relative sensitivities on temperature for 523/542, 485/542, and 793/840 emission intensity ratios were 1.06 ± 0.02, 2.03 ± 0.23, and 0.98 ± 0.10%K⁻¹ with temperature resolutions of 0.3, 0.7, and 1.8 K, respectively. The study showed that the higher relative temperature sensitivity does not necessarily lead to the more precise temperature measurement and better resolution, since it may be compromised by a larger uncertainty in measurement of low-intensity emission bands. Full article

(This article belongs to the Special Issue Luminescent Rare-Earth-Based Nanomaterials)

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20 pages, 5325 KiB

Open AccessArticle

Making Nd³⁺ a Sensitive Luminescent Thermometer for Physiological Temperatures—An Account of Pitfalls in Boltzmann Thermometry

by Markus Suta, Željka Antić, Vesna Ðorđević, Sanja Kuzman, Miroslav D. Dramićanin and Andries Meijerink

Nanomaterials 2020, 10(3), 543; https://0-doi-org.brum.beds.ac.uk/10.3390/nano10030543 - 18 Mar 2020

Cited by 94 | Viewed by 5798

Abstract

Ratiometric luminescence thermometry employing luminescence within the biological transparency windows provides high potential for biothermal imaging. Nd³⁺ is a promising candidate for that purpose due to its intense radiative transitions within biological windows (BWs) I and II and the simultaneous efficient excitability within BW I. This makes Nd³⁺ almost unique among all lanthanides. Typically, emission from the two ⁴F_3/2 crystal field levels is used for thermometry but the small ~100 cm⁻¹ energy separation limits the sensitivity. A higher sensitivity for physiological temperatures is possible using the luminescence intensity ratio (LIR) of the emissive transitions from the ⁴F_5/2 and ⁴F_3/2 excited spin-orbit levels. Herein, we demonstrate and discuss various pitfalls that can occur in Boltzmann thermometry if this particular LIR is used for physiological temperature sensing. Both microcrystalline, dilute (0.1%) Nd³⁺-doped LaPO₄ and LaPO₄: x% Nd³⁺ (x = 2, 5, 10, 25, 100) nanocrystals serve as an illustrative example. Besides structural and optical characterization of those luminescent thermometers, the impact and consequences of the Nd³⁺ concentration on their luminescence and performance as Boltzmann-based thermometers are analyzed. For low Nd³⁺ concentrations, Boltzmann equilibrium starts just around 300 K. At higher Nd³⁺ concentrations, cross-relaxation processes enhance the decay rates of the ⁴F_3/2 and ⁴F_5/2 levels making the decay faster than the equilibration rates between the levels. It is shown that the onset of the useful temperature sensing range shifts to higher temperatures, even above ~ 450 K for Nd concentrations over 5%. A microscopic explanation for pitfalls in Boltzmann thermometry with Nd³⁺ is finally given and guidelines for the usability of this lanthanide ion in the field of physiological temperature sensing are elaborated. Insight in competition between thermal coupling through non-radiative transitions and population decay through cross-relaxation of the ⁴F_5/2 and ⁴F_3/2 spin-orbit levels of Nd³⁺ makes it possible to tailor the thermometric performance of Nd³⁺ to enable physiological temperature sensing. Full article

(This article belongs to the Special Issue Luminescent Rare-Earth-Based Nanomaterials)

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15 pages, 3148 KiB

Open AccessArticle

Synthesis, Cytotoxicity Assessment and Optical Properties Characterization of Colloidal GdPO₄:Mn²⁺, Eu³⁺ for High Sensitivity Luminescent Nanothermometers Operating in the Physiological Temperature Range

by Kamila Maciejewska, Blazej Poźniak, Marta Tikhomirov, Adrianna Kobylińska and Łukasz Marciniak

Nanomaterials 2020, 10(3), 421; https://0-doi-org.brum.beds.ac.uk/10.3390/nano10030421 - 28 Feb 2020

Cited by 19 | Viewed by 2634

Abstract

Herein, a novel synthesis method of colloidal GdPO₄:Mn²⁺,Eu³⁺ nanoparticles for luminescent nanothermometry is proposed. XRD, TEM, DLS, and zeta potential measurements confirmed the crystallographic purity and reproducible morphology of the obtained nanoparticles. The spectroscopic properties of GdPO₄:Mn²⁺,Eu³⁺ with different amounts of Mn²⁺ and Eu³⁺ were analyzed in a physiological temperature range. It was found that GdPO₄:1%Eu³⁺,10%Mn²⁺ nanoparticles revealed extraordinary performance for noncontact temperature sensing with relative sensitivity S_R = 8.88%/°C at 32 °C. Furthermore, the biocompatibility and safety of GdPO₄:15%Mn²⁺,1%Eu³⁺ was confirmed by cytotoxicity studies. These results indicated that colloidal GdPO₄ doped with Mn²⁺ and Eu³⁺ is a very promising candidate as a luminescent nanothermometer for in vitro applications. Full article

(This article belongs to the Special Issue Luminescent Rare-Earth-Based Nanomaterials)

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12 pages, 3749 KiB

Open AccessArticle

LiAl₅O₈:Fe³⁺ and LiAl₅O₈:Fe³⁺, Nd³⁺ as a New Luminescent Nanothermometer Operating in 1st Biological Optical Window

by Karolina Kniec, Marta Tikhomirov, Blazej Pozniak, Karolina Ledwa and Lukasz Marciniak

Nanomaterials 2020, 10(2), 189; https://0-doi-org.brum.beds.ac.uk/10.3390/nano10020189 - 22 Jan 2020

Cited by 31 | Viewed by 4000

Abstract

New types of contactless luminescence nanothermometers, namely, LiAl₅O₈:Fe³⁺ and LiAl₅O₈:Fe³⁺, Nd³⁺ are presented for the first time, revealing the potential for applications in biological systems. The temperature-sensing capability of the nanocrystals was analyzed in wide range of temperature (−150 to 300 °C). The emission intensity of the Fe³⁺ ions is affected by the change in temperature, which induces quenching of the ⁴T₁ (⁴G) → ⁶A₁ (⁶S) Fe³⁺ transition situated in the 1st biological window. The highest relative sensitivity in the temperature range (0 to 50 °C) was found to be 0.82% °C (at 26 °C) for LiAl₅O₈: 0.05% Fe³⁺ nanoparticles that are characterized by long luminescent lifetime of 5.64 ms. In the range of low and high temperatures the S_max was calculated for LiAl₅O₈:0.5% Fe³⁺ to be 0.92% °C at −100 °C and for LiAl₅O₈:0.01% Fe³⁺ to be 0.79% °C at 150 °C. The cytotoxicity assessment carried out on the LiAl₅O₈:Fe³⁺ nanocrystals, demonstrated that they are biocompatible and may be utilized for in vivo temperature sensing. The ratiometric luminescent nanothermometer, LiAl₅O₈:Fe³⁺, Nd³⁺, which was used as a reference, possesses an S_max = 0.56%/°C at −80 °C, upon separate excitation of Fe³⁺ and Nd³⁺ ions using 266 nm and 808 nm light, respectively. Full article

(This article belongs to the Special Issue Luminescent Rare-Earth-Based Nanomaterials)

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