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.

Stokes and anti-Stokes luminescence in Tm(3+)/Yb(3+)-doped Lu3Ga5O12 nano-garnets: a study of multipolar interactions and energy transfer dynamics.

Nanocrystalline Lu3Ga5O12 garnets doped with Tm(3+)/Yb(3+) ions have been synthesized by a low cost and environmentally benign sol-gel technique and characterized for their structural, Stokes and anti-Stokes luminescence properties. The diffuse reflectance spectra of doped Lu3Ga5O12 nano-garnets have been measured to derive the partial energy level structure of Tm(3+) and Yb(3+) ions and possible energy transfer channels between them. Upon laser excitation at 473 nm, weak red and intense near-infrared Stokes emissions have been observed in the nano-garnets. The decay curves of (3)H4 and (1)G4 levels of Tm(3+) ions and the (2)F5/2 level of Yb(3+) ions have been measured upon resonant laser excitation and are found to be non-exponential in nature due to multipolar interactions. In order to know the kind of multipolar interaction among optically active ions, the decay curves are analyzed through the generalized Yokota-Tanimoto model. Moreover, under 970 nm laser excitation, intense blue anti-Stokes emission is observed by the naked eye in Tm(3+)-Yb(3+) co-doped Lu3Ga5O12 nano-garnets. The results show that as-synthesized nano-garnets may be useful in the field of phosphors and photonics.

Infrared-to-Visible Light Conversion in Er(3+) -Yb(3+) :Lu3 Ga5 O12 Nanogarnets.

Er(3+) -Yb(3+) co-doped Lu3 Ga5 O12 nanogarnets were prepared and characterized; their structural and luminescence properties were determined as a function of the Yb(3+) concentration. The morphology of the nanogarnets was studied by HRTEM. Under 488 nm excitation, the nanogarnets emit green, red, and near-infrared light. The decay curves for the ((4) S3/2 , (2) H11/2 ) and (4) F9/2 levels of the Er(3+) ions exhibit a non-exponential nature under resonant laser excitation and their effective lifetimes are found to decrease with an increase in the Yb(3+) concentration from 1.0 to 10.0 mol %. The non-exponential decay curves are well fitted to the Inokuti-Hirayama model for S=8, indicating that the mechanism of interaction for energy transfer between the optically active ions is of dipole-quadrupole type. Upon 976 nm laser excitation, an intense green upconverted emission is clearly observed by the naked eyes. A significant enhancement of the red-to-green intensity ratio of Er(3+) ions was observed with an increase in Yb(3+) concentration. The power dependence and the dynamics of the upconverted emission confirm the existence of two-photon upconversion processes for the green and red emissions.

Pressure-Induced Remarkable Spectral Red-Shift in Mn2+ -Activated NaY9 (SiO4 )6 O2 Red-Emitting Phosphors for High-Sensitive Optical Manometry.

To settle the low sensitivity of luminescent manometers, the Mn2+ -activated NaY9 (SiO4 )6 O2 red-emitting phosphors with splendid pressure sensing performances are developed. Excited by 408 nm, the resulting products emit bright red emission originating from 4 T1 (4 G) → 6 A1 transition of Mn2+ , in which the optimal concentration of the activator ion is ≈1 mol%. Moreover, the admirable thermal stability of the developed phosphors is studied and confirmed by the temperature-dependent emission spectra, based on which the activation energy is derived to be 0.275 eV. By analyzing the pressure-dependent Raman spectra, the structural stability of the synthesized compounds at extreme conditions is verified. Furthermore, the designed phosphors exhibit remarkable spectral red-shift at elevated pressure. Especially, as pressure increases from 0.75 to 7.16 GPa, the emission band centroid shifts from 617.2 to 663.4 nm, resulting in a high sensitivity (dλ/dP) of 7.00 nm GPa-1 , whereas the full width at half maximum (FWHM) increases from 83.0 to 110.6 nm, leading to the ultra-high sensitivity (dFWHM/dP) of 10.13 nm GPa-1 . These achievements manifest that the designed red-emitting phosphors are appropriate for ultrasensitive optical manometry. More importantly, the developed manometer is a current global leader in sensitivity, when operating in the band-width mode, that is, FWHM.

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.

White light generation in Dy(3+)-doped oxyfluoride glass and transparent glass-ceramics containing CaF2 nanocrystals.

The radiative emission properties of the Dy3+ ions in an oxyfluoride glass and glass-ceramics have been studied for the generation of white light. The x-ray diffraction pattern of the glass-ceramics shows the formation of CaF2 fluorite-type nanocrystals in the glass matrix after a suitable thermal treatment of the precursor glass, whereas time-resolved optical measurements show the incorporation of the Dy3+ ions in the CaF2 nanocrystals. Intense white light has been observed when the samples are excited with 451 nm laser light. From the visible emission spectra, yellow to blue intensity ratios and the chromaticity color coordinates have been determined. All the color coordinates are found to lie in the white light region of the chromaticity color diagram.

Stokes and upconverted luminescence in Er3+/Yb3+-doped Y3Ga5O12 nano-garnets.

The green, red, near-infrared and near-infrared-to-visible upconverted luminescence properties of Er3+/Yb3+ codoped Y3Ga5O12 nanocrystalline powders have been studied using laser spectroscopy. A diffuse reflectance and luminescence spectra confirm that Er3+ and Yb3+ ions occupy the Y3+ sites of the single-phase cubic nano-garnet. Very bright green and red luminescence of the Er3+ ions are detected by the naked eyes, even for a laser power as low as 15 mW, when the Yb3+ ions are excited at 970 nm. The red upconverted emission is more intense than that under direct excitation of the Er3+ ions. The power dependence and the dynamics of the near-infrared-to-green and near-infrared-to-red upconverted emissions show the existence of different two-photon energy transfer upconversion processes. The results here presented indicate that Er3+/Yb3+ codoped Y3Ga5O12 can be a good candidate as an optical nanoheater and nanothermometer in biomedicine applications in the first biological window.

Lanthanide Upconverted Luminescence for Simultaneous Contactless Optical Thermometry and Manometry-Sensing under Extreme Conditions of Pressure and Temperature.

The growing interest in the miniaturization of various devices and conducting experiments under extreme conditions of pressure and temperature causes the need for the development of small, contactless, precise, and accurate optical sensors without any electrical connections. In this work, YF3:Yb3+-Er3+ upconverting microparticles are used as a bifunctional luminescence sensor for simultaneous temperature and pressure measurements. Different changes in the properties of Er3+ green and red upconverted luminescence, after excitation of Yb3+ ions in the near-infrared at ∼975 nm, are used to calibrate pressure and/or temperature inside the hydrostatic chamber of a diamond anvil cell (DAC). For temperature sensing, changes in the relative intensities of the Er3+ green upconverted luminescence of 2H11/2 and 4S3/2 thermally coupled multiplets to the 4I15/2 ground state, whose relative populations follow a Boltzmann distribution, are calibrated. For pressure sensing, the spectral shift of the Er3+ upconverted red emission peak at ∼665 nm, between the Stark sublevels of the 4F9/2 → 4I15/2 transition, is used. Experiments performed under simultaneous extreme conditions of pressure, up to ∼8 GPa, and temperature, up to ∼473 K, confirm the possibility of remote optical pressure and temperature sensing.

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.

Structural study of the Eu3+ environments in fluorozirconate glasses: role of the temperature-induced and the pressure-induced phase transition processes in the development of a rare earth's local structure model.

The correlation between the optical properties of the Eu(3+) ions and their local structures in fluorozirconate glasses and glass-ceramics have been analyzed by means of steady-state and time-resolved site-selective laser spectroscopies. Changes in the crystal-field interaction, ranging from weak to medium strength values, are observed monitoring the luminescence and the lifetime of the Eu(3+) ions in different local environments in the glass. As key roles in this study, the Eu(3+) luminescence in the thermally-induced crystallization of the glass and the pressure-induced amorphization of the crystalline phase of the glass-ceramic experimentally states the existence of a parent local structure for the Eu(3+) ions in the glass, identified as the EuZrF(7) crystalline phase. Starting from the ab initio single overlap model, crystal-field calculations have been performed in the glass and the glass-ceramic. From the site-selective measurements, the crystal-field parameters sets are obtained, giving a suitable simulation of the (7)F(J) (J=0-6) Stark energy level diagram for the Eu(3+) ions in the different environments present in the fluorozirconate glass. A simple geometrical model based on a continuous distortion of the parent structure is proposed for the distribution of local environments of the Eu(3+) ions in the fluorozirconate glass.

Multifunctional Optical Sensors for Nanomanometry and Nanothermometry: High-Pressure and High-Temperature Upconversion Luminescence of Lanthanide-Doped Phosphates-LaPO4/YPO4:Yb3+-Tm3.

Upconversion luminescence of nano-sized Yb3+ and Tm3+ codoped rare earth phosphates, that is, LaPO4 and YPO4, has been investigated under high-pressure (HP, up to ∼25 GPa) and high-temperature (293-773 K) conditions. The pressure-dependent luminescence properties of the nanocrystals, that is, energy red shift of the band centroids, changes of the band ratios, shortening of upconversion lifetimes, and so forth, make the studied nanomaterials suitable for optical pressure sensing in nanomanometry. Furthermore, thanks to the large energy difference (∼1800 cm-1), the thermalized states of Tm3+ ions are spectrally well-separated, providing high-temperature resolution, required in optical nanothermometry. The temperature of the system containing such active nanomaterials can be determined on the basis of the thermally induced changes of the Tm3+ band ratio (3F2,3 → 3H6/3H4 → 3H6), observed in the emission spectra. The advantage of such upconverting optical sensors is the use of near-infrared light, which is highly penetrable for many materials. The investigated nanomanometers/nanothermometers have been successfully applied, as a proof-of-concept of a novel bimodal optical gauge, for the determination of the temperature of the heated system (473 K), which was simultaneously compressed under HP (1.5 and 5 GPa).

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.