The use of energy looping between Tm3+ and Er3+ ions to obtain an intense upconversion under the 1208 nm radiation and its use in temperature sensing.

The upconversion phenomenon allows for the emission of nanoparticles (NPs) under excitation with near-infrared (NIR) light. Such property is demanded in biology and medicine to detect or treat diseases such as tumours. The transparency of biological systems for NIR light is limited to three spectral ranges, called biological windows. However, the most frequently used excitation laser to obtain upconversion is out of these ranges, with a wavelength of around 975 nm. In this article, we show an alternative - Tm3+/Er3+-doped NPs that can convert 1208 nm excitation radiation, which is in the range of the 2nd biological window, to visible light within the 1st biological window. The spectroscopic properties of the core@shell NaYF4:Tm3+@NaYF4 and NaYF4:Er3+,Tm3+@NaYF4 NPs revealed a complex mechanism responsible for the observed upconversion. To explain emission in the studied NPs, we propose an energy looping mechanism: a sequence of ground state absorption, energy transfers and cross-relaxation (CR) processes between Tm3+ ions. Next, the excited Tm3+ ions transfer the absorbed energy to Er3+ ions, which results in green, red and NIR emission at 526, 546, 660, 698, 802 and 982 nm. The ratio between these bands is temperature-dependent and can be used in remote optical thermometers with high relative temperature sensitivity, up to 2.37%/°C at 57 °C. The excitation and emission properties of the studied NPs fall within 1st and 2nd biological windows, making them promising candidates for studies in biological systems.

Ultralow pressure sensing and luminescence thermometry based on the emissions of Er3+/Yb3+ codoped Y2Mo4O15 phosphors.

Pressure and temperature are fundamental physical parameters, so their monitoring is crucial for various industrial and scientific purposes. For this reason, we developed a new optical sensor material that allows monitoring of both the physical parameters. The synthesized material exhibits upconversion (UC) emission of Er3+ in the red and green spectral regions under NIR (975 nm) laser irradiation. These UC emissions are strongly temperature-dependent, allowing multimode temperature sensing, either based on the luminescence intensity ratio between thermal-coupled energy levels (TCLs) or non-thermal-coupled energy levels (NTCLs) of Er3+ ions. Meanwhile, the luminescence lifetime of the 4S3/2 state of Er3+ ions was used as the third temperature-dependent spectroscopic parameter, enabling multi-parameter thermal sensing. Moreover, the observed enhancement of laser-induced heating of the sample under vacuum conditions allows for the conversion of the luminescent thermometer into a remote vacuum sensor. The pressure variations in the system are correlated with changes in the band intensity ratio (525/550 nm) of Er3+ TCLs, which are further applied for optical, contactless vacuum sensing. This is because of the light-to-heat conversion effect, which is greatly enhanced under vacuum conditions and manifests as a change in the intensity ratio of Er3+ bands (525/550 nm). The obtained results indicate that an Y2Mo4O15:Er3+/Yb3+ (YMO) phosphor has great application potential for the development of multi-functional and non-invasive optical sensors of pressure and temperature.

Near-infrared optical nanothermometry via upconversion of Ho3+-sensitized nanoparticles.

Recently, materials revealing the upconversion (UC) phenomenon, which is a conversion of low-energy photons to higher-energy ones, have attracted considerable attention in luminescence thermometry due to the possibility of precise and remote optical thermal sensing. The most widely studied type of luminescent thermometry uses a ratiometric approach based on changes in the UC luminescence intensity, mainly of lanthanide ions' thermally coupled energy levels. In this work, NaYF4:Ho3+@NaYF4, and NaYF4:Ho3+, Er3+@NaYF4 nanoparticles (NPs) were synthesized by the controlled reaction in oleic acid and octadecene at 573 K. The obtained nanoparticles had hexagonal structures, oval shapes, and average sizes of 22.5 ± 2.2 nm and 22.2 ± 2.0 nm, respectively. The spectroscopic properties of the products were investigated by measurements of the UC emission under 1151 nm laser excitation in the temperature range between 295 to 378 K. The sample doped with Ho3+ and Er3+ ions showed unique behavior of enhancing emission intensity with the temperature. The relative sensitivity determined for the NPs containing Ho3+ and Er3+ ions, reached the maximum value of 1.80%/K at 378 K. Here, we prove that the NaYF4:Ho3+, Er3+@NaYF4 system presents unique and excellent optical temperature sensing properties based on the luminescence intensity ratios of the near-infrared bands of both Ho3+ and Er3+ ions.

Exploring Ln(III)-Ion-Based Luminescent Species as Down-Shifters for Photovoltaic Solar Cells.

In this work, we have compiled our research on lanthanide-based luminescent materials for use as down-shifter layers in photovoltaic (PV) mini-modules. The complexes we have prepared (C1-17), with formulas [Eu2(phen)2(bz)6] (C1), [Eu2(bphen)2(bz)6] (C2), [Eu(tta)3bphen] (C3), [Eu(bta)3pyz-phen] (C4), [Eu(tta)3pyz-phen] (C5), [Eu(bta)3me-phen] (C6), [Er(bta)3me-phen] (C7), [Yb(bta)3me-phen] (C8), [Gd(bta)3me-phen] (C9), [Yb(bta)3pyz-phen] (C10), [Er(tta)3pyz-phen] (C11), [Eu2(bz)4(tta)2(phen)2] (C12), [Gd2(bz)4(tta)2(phen)2] (C13), [EuTb(bz)4(tta)2(phen)2] (C14), [EuGd(bz)4(tta)2(phen)2] (C15), [Eu1.2Gd0.8(bz)4(tta)2(phen)2] (C16), and [Eu1.6Gd0.4(bz)4(tta)2(phen)2] (C17), can be grouped into three families based on their composition: Complexes C1-6 were synthesized using Eu3+ ions and phenanthroline derivatives as the neutral ligands and fluorinated ß-diketonates as the anionic ligands. Complexes C7-11 were prepared with ligands similar to those of complexes C1-6 but were synthesized with Er3+, Yb3+, or Gd3+ ions. Complexes C12-17 have the general formula [M1M2(bz)4(tta)2(phen)2], where M1 and M2 can be Eu3+, Gd3+, or Tb3+ ions, and the ligands were benzoate (bz-), 2-thenoyltrifluoroacetone (tta-), and 1,10-phenanthroline (phen). Most of the complexes were characterized using X-ray techniques, and their photoluminescent properties were studied. We then assessed the impact of complexes in the C1-6 and C12-17 series on the EQE of PV mini-modules and examined the durability of one of the complexes (C6) in a climate chamber when embedded in PMMA and EVA films. This study emphasizes the methodology employed and the key findings, including enhanced mini-module efficiency. Additionally, we present promising results on the application of complex C6 in a bifacial solar cell.

Mechanoluminescence and Photoluminescence Heterojunction for Superior Multimode Sensing Platform of Friction, Force, Pressure, and Temperature in Fibers and 3D-Printed Polymers.

Endowing a single material with various types of luminescence, that is, exhibiting a simultaneous optical response to different stimuli, is vital in various fields. A photoluminescence (PL)- and mechanoluminescence (ML)-based multifunctional sensing platform is built by combining heterojunctioned ZnS/CaZnOS:Mn2+ mechano-photonic materials using a 3D-printing technique and fiber spinning. ML-active particles are embedded in micrometer-sized cellulose fibers for flexible optical devices capable of emitting light driven by mechanical force. Individually modified 3D-printed hard units that exhibit intense ML in response to mechanical deformation, such as impact and friction, are also fabricated. Importantly, they also allow low-pressure sensing up to ≈100 bar, a range previously inaccessible by any other optical sensing technique. Moreover, the developed optical manometer based on the PL of the materials demonstrates a superior high-pressure sensitivity of ≈6.20 nm GPa-1 . Using this sensing platform, four modes of temperature detection can be achieved: excitation-band spectral shifts, emission-band spectral shifts, bandwidth broadening, and lifetime shortening. This work supports the possibility of mass production of ML-active mechanical and optoelectronic parts integrated with scientific and industrial tools and apparatus.

Noncentrosymmetric Lanthanide-Based MOF Materials Exhibiting Strong SHG Activity and NIR Luminescence of Er3+: Application in Nonlinear Optical Thermometry.

Optically active luminescent materials based on lanthanide ions attract significant attention due to their unique spectroscopic properties, nonlinear optical activity, and the possibility of application as contactless sensors. Lanthanide metal-organic frameworks (Ln-MOFs) that exhibit strong second-harmonic generation (SHG) and are optically active in the NIR region are unexpectedly underrepresented. Moreover, such Ln-MOFs require ligands that are chiral and/or need multistep synthetic procedures. Here, we show that the NIR pulsed laser irradiation of the noncentrosymmetric, isostructural Ln-MOF materials (MOF-Er3+ (1) and codoped MOF-Yb3+/Er3+ (2)) that are constructed from simple, achiral organic substrates in a one-step procedure results in strong and tunable SHG activity. The SHG signals could be easily collected, exciting the materials in a broad NIR spectral range, from ≈800 to 1500 nm, resulting in the intense color of emission, observed in the entire visible spectral region. Moreover, upon excitation in the range of ≈900 to 1025 nm, the materials also exhibit the NIR luminescence of Er3+ ions, centered at ≈1550 nm. The use of a 975 nm pulse excitation allows simultaneous observations of the conventional NIR emission of Er3+ and the SHG signal, altogether tuned by the composition of the Ln-MOF materials. Taking the benefits of different thermal responses of the mentioned effects, we have developed a nonlinear optical thermometer based on lanthanide-MOF materials. In this system, the SHG signal decreases with temperature, whereas the NIR emission band of Er3+ slightly broadens, allowing ratiometric (Er3+ NIR 1550 nm/SHG 488 nm) temperature monitoring. Our study provides a groundwork for the rational design of readily available and self-monitoring NLO-active Ln-MOFs with the desired optical and electronic properties.

Europium(III)-Doped Gadolinium(III) Complex for High-Sensitivity Temperature Sensing in the Physiological Range.

A new Eu3+-doped Gd3+ complex of formula [Eu0.0135Gd0.9865(pta)3me-phen] was synthesized and structurally characterized (Hpta = benzoyltrifluoroacetone, me-phen = 5-methyl-1,10-phenanthroline). The photoluminescence study revealed that when the compound was excited at RT, under a 457 nm continuous laser, the material exhibited high luminescence due to the antenna effect of the ligands, as well as a good balance between the phosphorescence from the spin-forbidden triplet (from the organic ligands), and the characteristic lanthanide f-f transitions. The ratio between the previous emissions drastically changed when the sample was heated up to 62 °C inside a tubular furnace. This ratio was investigated using the luminescence intensity ratio method, to analyze the capabilities of the sample as a temperature sensor. The relative sensitivity reached a maximum of 11.4 °C-1 %, maintaining a detection limit below 0.15 °C for the whole temperature range.

Experimental and Numerical Validation of Whispering Gallery Resonators as Optical Temperature Sensors.

This study experimentally and numerically validates the commonly employed technique of laser-induced heating of a material in optical temperature sensing studies. Furthermore, the Er3+-doped glass microspheres studied in this work can be employed as remote optical temperature sensors. Laser-induced self-heating is a useful technique commonly employed in optical temperature sensing research when two temperature-dependent parameters can be correlated, such as in fluorescence intensity ratio vs. interferometric calibration, allowing straightforward sensor characterization. A frequent assumption in such experiments is that thermal homogeneity within the sensor volume, that is, a sound hypothesis when dealing with small volume to surface area ratio devices such as microresonators, but has never been validated. In order to address this issue, we performed a series of experiments and simulations on a microsphere supporting whispering gallery mode resonances, laser heating it at ambient pressure and medium vacuum while tracking the resonance wavelength shift and comparing it to the shift rate observed in a thermal bath. The simulations were done starting only from the material properties of the bulk glass to simulate the physical phenomena of laser heating and resonance of the microsphere glass. Despite the simplicity of the model, both measurements and simulations are in good agreement with a highly homogeneous temperature within the resonator, thus validating the laser heating technique.

Multifunctional cellulose fibers: Intense red upconversion under 1532 nm excitation and temperature-sensing properties.

The unique properties of upconverting nanoparticles are responsible for their various applications in photonic materials, medicine, analytics, or energy conversion. In this work, the NaErF4:Tm3+@NaYF4 core@shell nanoparticles were synthesized by reaction in high-boiling point solvents and incorporated into cellulose fibers. Nanoparticles showed intense upconversion under 1532 nm excitation wavelength due to Er3+ in their structure. Additional co-doping with Tm3+ ions allowed to shift of the typical green luminescence of Er3+ ions to red especially demanded in anti-counterfeiting applications. The products' composition, morphology, and structure parameters confirmed their requested properties. The article demonstrates that cellulose fibers are suitable carriers of NaErF4:Tm3+@NaYF4 NPs. We also show that the temperature-dependent emission of Er3+ ions allows for the preparation of temperature-sensing cellulose fibers.

A novel optical thermometry strategy based on emission of Tm3+/Yb3+ codoped Na3GdV2O8 phosphors.

In the last few years, huge progress has been made in the development of remote optical thermometry strategies, due to their non-contact, high-sensitivity and fast measurement characteristics, which are especially important for various industrial and bio-applications. For these purposes, lanthanide-doped particles seem to be the most promising luminescence thermometers. In this study, Tm3+/Yb3+:Na3GdV2O8 (NGVO) phosphors were prepared using a sol-gel method. Under 980 nm excitation, the upconversion (UC) and down-shifting (DS) emission spectra are composed of two visible emission bands arising from the Tm3+ transitions 1G4 → 3H6 (475 nm) and 1G4 → 3F4 (651 nm), a strong emission at 800 nm (3H4 → 3H6) in the first biological window and emission in the third biological window at 1625 nm (3F4 → 3H6), respectively. Accordingly, the luminescence intensity ratio (LIR) between the Tm3+ LIR1 (800/475) and LIR2 (1625/475) transitions demonstrates excellent relative sensing sensitivity values (4.2% K-1-2% K-1) and low-temperature uncertainties (0.4 K-0.5 K) over a wide temperature sensing range of 300 K to 565 K, which are remarkably better than those of many other luminescence thermometers. This phosphor exhibits strong NIR emission at low excitation density, meaning that it has potential uses in deep tissue imaging, optical signal amplification and other fields. The results indicate that Tm3+/Yb3+:NGVO is an ideal candidate for thermometers and particularly for biological applications.

Highly luminescent mixed-ligand bimetallic lanthanoid(III) complexes for photovoltaic applications.

Six new mixed-ligand bimetallic complexes [Eu2(bz)4(tta)2(phen)2] (1), [Gd2(bz)4(tta)2(phen)2] (2), [EuTb(bz)4(tta)2(phen)2] (3), [EuGd(bz)4(tta)2(phen)2] (4), [Eu1,2Gd0,8(bz)4(tta)2(phen)2] (5) and [Eu1,6Gd0,4(bz)4(tta)2(phen)2] (6) have been prepared with the Eu3+, Gd3+ and Tb3+ ions and the benzoate (bz-), 2-thenoyltrifluoroacetonate (tta-) and the 1,10-phenanthroline (phen) ligands. The compounds combine highly efficient antennas to obtain highly luminescent complexes to enhance solar cell efficiency. The benzoate ligand has been chosen to take its advantage as a bridging ligand to end up with bimetallic complexes to study the effect of combining two metal ions in the luminescent molecule. The structure of 1 was obtained by single-crystal X-ray diffraction, and 1-6 were found to be isostructural by powder X-ray diffraction analysis. The photophysical properties were studied by the absorbance and emission spectra and emission lifetimes. The magnetic properties of 2 were studied, and we found intramolecular antiferromagnetic interactions between the Gd3+ ions. We prepared luminescent down-shifting layers (LDSL) with the 1, 3-6 complexes embedded in ethylene-vinyl-acetate and studied their effect in the external quantum efficiency (EQE) and intensity-voltage (I-V) plots of a solar mini-module. We found that LDSL containing the bimetallic complexes 3 and 6 enhance the efficiency of the solar mini-module from 11.26(3)% to 11.76(4)% (+0.52%) and to 11.44(2)% (+0.21%), respectively.

Luminescent Nanothermometer Operating at Very High Temperature-Sensing up to 1000 K with Upconverting Nanoparticles (Yb3+/Tm3+).

Lanthanide-based luminescent nanothermometers play a crucial role in optical temperature determination. However, because of the strong thermal quenching of the luminescence, as well as the deterioration of their sensitivity and resolution with temperature elevation, they can operate in a relatively low-temperature range, usually from cryogenic to ≈800 K. In this work, we show how to overcome these limitations and monitor very high-temperature values, with high sensitivity (≈2.1% K-1) and good thermal resolution (≈1.4 K) at around 1000 K. As an optical probe of temperature, we chose upconverting Yb3+-Tm3+ codoped YVO4 nanoparticles. For ratiometric sensing in the low-temperature range, we used the relative intensities of the Tm3+ emissions associated with the 3F2,3 and 3H4 thermally coupled levels, that is, 3F2,3 → 3H6/3H4 → 3H6 (700/800 nm) band intensity ratio. In order to improve sensitivity and resolution in the high-temperature range, we used the 940/800 nm band intensity ratio of the nonthermally coupled levels of Yb3+ (2F5/2 → 2F7/2) and Tm3+ (3H4 → 3H6). These NIR bands are very intense, even at extreme temperature values, and their intensity ratio changes significantly, allowing accurate temperature sensing with high thermal and spatial resolutions. The results presented in this work may be particularly important for industrial applications, such as metallurgy, catalysis, high-temperature synthesis, materials processing and engineering, and so forth, which require rapid, contactless temperature monitoring at extreme conditions.

Inert Shell Effect on the Quantum Yield of Neodymium-Doped Near-Infrared Nanoparticles: The Necessary Shield in an Aqueous Dispersion.

Lanthanide-doped nanoparticles (LnNPs) are versatile near-infrared (NIR) emitting nanoprobes that have led to their growing interest for use in biomedicine-related imaging. Toward the brightest LnNPs, high photoluminescence quantum yield (PLQY) values are attained by implementing core/shell engineering, particularly with an optically inert shell. In this work, a thorough investigation is performed to quantify how an outer inert shell maintains the PLQY of Nd3+-doped LnNPs dispersed in an aqueous environment. Three relevant quantitative findings affecting the PLQY of Nd3+-doped LnNPs are identified: (i) the PLQY of core LnNPs is improved 3-fold upon inert shell coating; (ii) PLQY decreases with increasing Nd3+ doping despite the inert shell; and (iii) solvent quenching has a major influence on the PLQY of the LnNPs, though it is relatively lessened for high Nd3+ doping. Overall, we shed new light on the impact of the LnNP architecture on the NIR emission, as well as on the quenching effects caused by doping concentration and solvent molecules.

Visible and NIR emitting Yb(iii) and Er(iii) complexes sensitized by ß-diketonates and phenanthroline derivatives.

Five new complexes namely, [Er(bta)3(me-phen)] (1), [Yb(bta)3(me-phen)] (2), [Gd(bta)3(me-phen)] (3), [Yb(bta)3(pyz-phen)] (4), and [Er(tta)3(pyz-phen)] (5) have been prepared with the fluorinated ß-diketone ligands Hbta and Htta (Hbta = benzoyltrifluoroacetone and Htta = 2-thenoyltrifluoroacetone) combined with the azacyclo phenanthroline-derivatives, 5-methyl-1,10-phenanthroline (me-phen) and pyrazino[2,3-f][1,10]phenanthroline (pyz-phen). The crystal structures of 2, 4 and 5 have been solved by single-crystal X-ray diffraction. PXRD patterns show that 1-3 are isostructural. All the compounds exhibit a molecular structure with the metal atom in an eight-coordination geometry. The photophysical processes involved in the photoluminescence of the complexes are investigated; as a result, the radiative lifetimes (τ Ln), the 4f-4f emission quantum efficiencies (Φ Ln) and the energy-levels diagram are calculated.

High pressure luminescence of Nd3+ in YAlO3 perovskite nanocrystals: A crystal-field analysis.

Pressure-induced energy blue- and red-shifts of the 4F3/2 → 4I9/2,11/2 near-infrared emission lines of Nd3+ ions in YAlO3 perovskite nano-particles have been measured from ambient conditions up to 29 GPa. Different positive and negative linear pressure coefficients have been calibrated for the emission lines and related to pressure-induced changes in the interactions between those Nd3+ ions and their twelve oxygen ligands at the yttrium site. Potentiality of the simple overlap model, combined with ab initio structural calculations, in the description of the effects of these interactions on the energy levels and luminescence properties of the optically active Nd3+ ion is emphasized. Simulations show how the energies of the 4f3 ground configuration and the barycenters of the multiplets increase with pressure, whereas the Coulomb interaction between f-electrons decreases and the crystal-field strength increases. All these effects combined explain the wavelength blue-shifts of some near-infrared emission lines of Nd3+ ions. Large pressure rates of various emission lines suggest that a YAlO3 perovskite nano-crystal can be a potential candidate for near-infrared optical pressure sensors.

Liquid whispering-gallery-mode resonator as a humidity sensor.

We experimentally demonstrate the high sensitivity of a novel liquid state, whispering-gallery-mode optical resonator to humidity changes. The optical resonator used consists of a droplet made of glycerol, a transparent liquid that enables high optical quality factor, doped with fluorescent material. As glycerol is highly hygroscopic, the refractive index and radius of the droplet change with ambient humidity. This produces a shift on the whispering gallery mode's wavelengths, which modulates the emission of the fluorescent material. This device shows an unpreceded sensitivity of 10-3 per relative humidity percent.

Regular oscillations and random motion of glass microspheres levitated by a single optical beam in air.

We experimentally report on optical binding of many glass particles in air that levitate in a single optical beam. A diversity of particle sizes and shapes interact at long range in a single Gaussian beam. Our system dynamics span from oscillatory to random and dimensionality ranges from 1 to 3D. The low loss for the center of mass motion of the beads could allow this system to serve as a standard many body testbed, similar to what is done today with atoms, but at the mesoscopic scale.

Regular oscillations and random motion of glass microspheres levitated by a single optical beam in air: publisher's note.

This publisher's note amends a recent publication [Opt. Express24(3), 2850-2857 (2016)] to include Acknowledgments.

Structure and NIR-luminescence of ytterbium(III) beta-diketonate complexes with 5-nitro-1,10-phenanthroline ancillary ligand: assessment of chain length and fluorination impact.

Seven new tris(ß-diketonear-nate)ytterbium(III) complexes with the general formula [Yb(ß-diketonate)3(5NO2phen)] (where the ß-diketone is either 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedione, 2,4-hexanedione or 2,6-dimethyl-3,5-heptanedione, and 5NO2phen = 5-nitro-1,10-phenanthroline) were synthesized and characterized by elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy and photoluminescence spectroscopy. Single crystal X-ray structures have been determined for three fluorinated complexes and ground state geometries of the other four complexes have been predicted using the Sparkle/PM6 model. These experimental structures and those designed by semi-empirical models reveal octacoordination around the Yb(3+) ion. Photoluminescence studies and lifetime measurements show that the increase in the fluorinated ß-diketonate chain length is associated with a decrease in Yb(3+) luminescence intensity of the (2)F5/2→(2)F7/2 transition at around 980 nm and the (2)F5/2 excited state lifetime, while the ligand lifetime value remains almost unaffected. Finally, fluorination of the ligands is only advised when the complexes are to be used for co-doping with isostructural Er(3+) complexes for optical amplifiers, since it leads to a slight decrease in luminescence intensity for the same ß-diketonate chain length.