Search Results (21)

Sr₂LaF₇:xPr³⁺ (x = 0.2, 1, 2, 3, 5, 10, and 25 mol%) nanophosphors with a cubic Fm3m structure were hydrothermally synthesized, forming nearly spherical nanoparticles with an average diameter of approximately 32 nm. Diffuse reflectance measurement and excitation spectra showed a primary excitation peak of Pr³⁺ at 443 nm, corresponding to the ground state to the ³P₂ level transition. Upon blue light excitation, Pr³⁺-activated Sr₂LaF₇ nanophosphors showed rich emission structure across the visible region of the spectrum, with blue (~483 nm), green (~525 nm), orange (~600 nm), and red (~640 nm) emissions, blue and orange being the most prominent ones. The relative intensities of these emissions varied with Pr³⁺ concentration, leading to tunable emission colors. The chromaticity showed slight variation with the Pr³⁺ content (0.350 < x < 0.417, 0.374 < y < 0.380), while the CCT value increased from 3118 K to 4901 K as the doping concentration increased. The optimized Sr₂LaF₇ with 2 mol% Pr³⁺ had the most intense emission with correlated color temperature (CCT) of 3628 K, corresponding to the warm white color. The proposed Pr³⁺-doping strategy offers valuable insights into discovering or optimizing single-phase phosphors for white-light-emitting applications. Full article

This paper addresses the upconversion of blue light to ultraviolet-C (UVC) with Pr³⁺-activated materials for antibacterial applications of UVC. It discusses the processes through which UV radiation provides biocidal effects on microorganisms, along with the most popular UVC sources employed in these processes. We describe the electronic and optical properties of the Pr³⁺ ion, emphasizing the conditions the host material must meet to obtain broad and intense emission in the UVC from parity-allowed transitions from the 4f5d levels and provide a list of materials that fulfill these conditions. This paper also delineates lanthanide-based upconversion, focusing on Pr³⁺ blue to UVC upconversion via the ³P₀ and ¹D₂ intermediate states, and suggests routes for improving the quantum efficiency of the process. We review literature related to the use of upconversion materials in antimicrobial photodynamic treatments and for the blue to UVC upconversion germicidal effects. Further, we propose the spectral overlap between the UVC emission of Pr³⁺ materials and the germicidal effectiveness curve as a criterion for assessing the potential of these materials in antimicrobial applications. Finally, this paper briefly assesses the toxicity of materials commonly used in the preparation of upconversion materials. Full article

The optical properties of Mn⁵⁺ ions, which are responsible for the intense green–turquoise–blue coloration of Mn⁵⁺-based pigments and the near-infrared emission of phosphors, are the focus of this article. Mn⁵⁺ ions enter crystalline matrices in four-fold coordinated positions and can maintain their 5+ valence state when crystalline hosts meet the conditions described in this work. Mn⁵⁺ ions have [Ar]3d² electronic configuration and always experience a strong crystal field due to a high electric charge; therefore, their lower electronic states have the ³A₂ < ¹E < ¹A₁ < ³T₂ < ³T₁ progression in energy. We present the properties of several Mn⁵⁺-based pigments and discuss the electronic transitions responsible for their coloration. Specifically, we show that the color is determined by the spin-allowed ³A₂ → ³T₁(³F) absorption, which extends across the orange–red–deep red spectral region and is strongly influenced by crystal field strength. The narrow-band emission Mn⁵⁺-activated near-infrared phosphors arise from the spin-forbidden ¹E → ³A₂ transition, whose energy is independent of the crystal field strength and determined by the nephelauxetic effect. We demonstrate the linear relationship between ¹E state energy and the nephelauxetic parameter β₁ using Racah parameter literature data for Mn⁵⁺ phosphors. Lastly, we address the recent applications of these Mn⁵⁺ phosphors in luminescence thermometry. Full article

Over the past three decades, luminescence thermometry has gained significant attention among researchers and practitioners. The method has progressed in terms of utilizing temperature-sensitive luminescent materials, obtaining temperature read-outs from luminescence, developing applications, and improving performance. This paper reviews and critically analyzes routes for improving luminescence thermometry performance, in particular the sensitivity, accuracy, and precision of the method. These include the use of highly temperature-sensitive probes, temperature read-outs from luminescence with improved sensitivity, multiparameter temperature-reading methods, the applications of principal component analysis and artificial neural networks, and sensor fusion. Full article

Accurate temperature measurement is critical across various scientific and industrial applications, necessitating advancements in thermometry techniques. This study explores luminescence thermometry, specifically utilizing machine learning methodologies to enhance temperature sensitivity and accuracy. We investigate the performance of principal component analysis (PCA) on the Eu³⁺-doped Y₂Mo₃O₁₂ luminescent probe, contrasting it with the traditional luminescence intensity ratio (LIR) method. By employing PCA to analyze the full emission spectra collected at varying temperatures, we achieve an average accuracy (ΔT) of 0.9 K and a resolution (δT) of 1.0 K, significantly outperforming the LIR method, which yielded an average accuracy of 2.3 K and a resolution of 2.9 K. Our findings demonstrate that while the LIR method offers a maximum sensitivity (Sr) of 5‰ K⁻¹ at 472 K, PCA’s systematic approach enhances the reliability of temperature measurements, marking a crucial advancement in luminescence thermometry. This innovative approach not only enriches the dataset analysis but also sets a new standard for temperature measurement precision. Full article

Detailed analysis covered the optical and structural properties of Eu³⁺-doped NaY₉Si₆O₂₆ oxyapatite phosphors, which were obtained via hydrothermal synthesis. X-ray diffraction patterns of NaY₉Si₆O₂₆:xEu³⁺ (x = 0, 1, 5, 7, 10 mol% Eu³⁺) samples proved a single-phase hexagonal structure (P63/m (176) space group). Differential thermal analysis showed an exothermic peak at 995 °C attributed to the amorphous to crystalline transformation of NaY₉Si₆O₂₆. Electron microscopy showed agglomerates composed of round-shaped nanoparticles ~53 nm in size. Room temperature photoluminescent emission spectra consisted of emission bands in the visible spectral region corresponding to ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) f-f transitions of Eu³⁺. Lifetime measurements showed that the Eu³⁺ concentration had no substantial effect on the rather long ⁵D₀-level lifetime. The Eu³⁺ energy levels in the structure were determined using room-temperature excitation/emission spectra. Using the ⁷F₁ manifold, the Nv-crystal field strength parameter was calculated to be 1442.65 cm⁻¹. Structural, electronic, and optical properties were calculated to determine the band gap value, density of states, and index of refraction. The calculated direct band gap value was 4.665 eV (local density approximation) and 3.765 eV (general gradient approximation). Finally, the complete Judd–Ofelt analysis performed on all samples confirmed the experimental findings. Full article

Tunable blue/red dual-emitting Eu³⁺-doped, Bi³⁺-sensitized SrF₂ phosphors were synthesized utilizing a solvothermal-microwave method. All phosphors have cubic structure (Fm-3m (225) space group) and well-distinct sphere-like particles with a size of ~20 nm, as examined by X-ray diffraction and transmission electron microscopy. The diffuse reflectance spectra reveal a redshift of the absorption band in the UV region as the Bi³⁺ concentration in SrF₂: Eu³⁺ phosphor increases. Under the 265 nm excitation, photoluminescence spectra show emission at around 400 nm from the host matrix and characteristic orange ⁵D₀ → ⁷F_1,2 and deep red ⁵D₀ → ⁷F₄ Eu³⁺ emissions. The red emission intensity increases with an increase in Bi³⁺ concentration up to 20 mol%, after which it decreases. The integrated intensity of Eu³⁺ red emission in the representative 20 mol% Bi³⁺ co-doped SrF₂:10 mol% Eu³⁺ shows twice as bright emission compared to the Bi³⁺-free sample. To demonstrate the potential application in LEDs for artificial light-based plant factories, the powder with the highest emission intensity, SrF₂: 10Eu, 20 Bi, was mixed with a ceramic binder and placed on top of a 275 nm UVC LED chip, showing pinkish violet light corresponding to blue (409 nm) and red (592, 614, and 700 nm) phosphors’ emission. Full article

A set of Eu³⁺-doped molybdates, Y₂₋xEuxMo₃O₁₂ (x = 0.04; 0.16; 0.2; 0.4; 0.8; 1; 1.6; 2), was synthesized using a solid-state technique and their properties studied as a function of Eu³⁺ concentration. X-ray diffraction showed that the replacement of Y³⁺ with larger Eu³⁺ resulted in a transformation from orthorhombic (low doping concentrations) through tetragonal (high doping concentrations), reaching monoclinic structure for full replacement in Eu₂Mo₃O₁₂. The intensity of typical Eu³⁺ red emission slightly increases in the orthorhombic structure then rises significantly with dopant concentration and has the highest value for the tetragonal Y₂Mo₃O₁₂:80mol% Eu³⁺. Further, the complete substitution of Y³⁺ with Eu³⁺ in the case of monoclinic Eu₂Mo₃O₁₂ leads to decreased emission intensity. Lifetime follows a similar trend; it is lower in the orthorhombic structure, reaching slightly higher values for the tetragonal structure and showing a strong decrease for monoclinic Eu₂Mo₃O₁₂. Temperature-sensing properties of the sample with the highest red Eu³⁺ emission, Y₂Mo₃O₁₂:80mol% Eu³⁺, were analyzed by the luminescence intensity ratio method. For the first time, the peak-sharpening algorithm was employed to separate overlapping peaks in luminescence thermometry, in contrast to the peak deconvolution method. The Sr (relative sensitivity) value of 2.8 % K⁻¹ was obtained at room temperature. Full article

The method of measuring temperature using luminescence by analyzing the emission spectra of Pr³⁺-doped YF₃ using principal component analysis is presented. The Pr³⁺-doped YF₃ is synthesized using a solid-state technique, and its single-phase orthorhombic crystal structure is confirmed using X-ray diffraction. The emission spectra measured within the 93–473 K temperature range displays characteristic Pr³⁺ f-f electronic transitions. The red emission from the ³P_0,1→³H₆,³F₂ electronic transition mostly dominates the spectra. However, at low temperatures, the intensity of the green emissions from the ³P_0,1→³H₅, deep-red ³P_0,1→³F₄, and the deep-red emissions from the ³P_0,1→³F₄ transitions are considerably lower compared to the intensity of the red emissions. Temperature variations directly impact the photoluminescent spectra, causing a notable increase in the green and deep-red emissions from the ³P₁ excited state. We utilized the entire spectrum as an input for principal component analysis, considering each temperature as an independent group of data. The first principal component explained 99.3% of the variance in emission spectra caused by temperature and we further used it as a reliable temperature indicator for luminescence thermometry. The approach has a maximum absolute sensitivity of around 0.012 K⁻¹. The average accuracy and precision values are 0.7 K and 0.5 K, respectively. Full article

Luminescence thermometry has emerged as a very versatile optical technique for remote temperature measurements, exhibiting a wide range of applicability spanning from cryogenic temperatures to 2000 K. This technology has found extensive utilization across many disciplines. In the last thirty years, there has been significant growth in the field of luminous thermometry. This growth has been accompanied by the development of temperature read-out procedures, the creation of luminescent materials for very sensitive temperature probes, and advancements in theoretical understanding. This review article primarily centers on luminescent nanoparticles employed in the field of luminescence thermometry. In this paper, we provide a comprehensive survey of the recent literature pertaining to the utilization of lanthanide and transition metal nanophosphors, semiconductor quantum dots, polymer nanoparticles, carbon dots, and nanodiamonds for luminescence thermometry. In addition, we engage in a discussion regarding the benefits and limitations of nanoparticles in comparison with conventional, microsized probes for their application in luminescent thermometry. Full article

To develop novel luminescent materials for optical temperature measurement, a series of Yb³⁺- and Er³⁺-doped Ca₃Sc₂Si₃O₁₂ (CSS) upconversion (UC) phosphors were synthesized by the sol–gel combustion method. The crystal structure, phase purity, and element distribution of the samples were characterized by powder X-ray diffraction and a transmission electron microscope (TEM). The detailed study of the photoluminescence emission spectra of the samples shows that the addition of Yb³⁺ can greatly enhance the emission of Er³⁺ by effective energy transfer. The prepared Yb³⁺ and Er³⁺ co-doped CSS phosphors exhibit green emission bands near 522 and 555 nm and red emission bands near 658 nm, which correspond to the ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2, and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺, respectively. The temperature-dependent behavior of the CSS:0.2Yb³⁺,0.02Er³⁺ sample was carefully studied by the fluorescence intensity ratio (FIR) technique. The results indicate the excellent sensitivity of the sample, with a maximum absolute sensitivity of 0.67% K⁻¹ at 500 K and a relative sensitivity of 1.34% K⁻¹ at 300 K. We demonstrate here that the temperature measurement performance of FIR technology using the CSS:Yb³⁺,Er³⁺ phosphor is not inferior to that of infrared thermal imaging thermometers. Therefore, CSS:Yb³⁺,Er³⁺ phosphors have great potential applications in the field of optical thermometry. Full article

The sensitivity of luminescent Boltzmann thermometers is restricted by the energy difference between the thermally coupled excitement levels of trivalent lanthanides, and their values further decrease with increases in temperature, rendering their use at high temperatures difficult. Here, we demonstrate how to overcome this sensitivity limitation by employing multiparameter and multilevel cascade temperature readings. For this purpose, we synthesized Dy³⁺:Y₂SiO₅, a phosphor whose emission is known to begin quenching at very high temperatures. Its photoluminescence-emission features, later used for thermometry, consisted of two blue emission bands centered around 486 nm and 458 nm, and two bands centered around 430 nm and 398 nm, which were only visible at elevated temperatures. Next, we performed thermometry using the standard luminescence-intensity ratio (LIR) method, which employs the ⁴F_9/2 and ⁴I_15/2 Dy³⁺ levels’ emissions and the multilevel cascade method, which additionally uses the ⁴G_11/2 level and overlapping intensities of ⁴I_13/2, ⁴M_21/2, ⁴K_17/2, and ⁴F_7/2 levels to create two LIRs with a larger energy difference than the standard LIR. This approach yielded a sensitivity that was 3.14 times greater than the standard method. Finally, we simultaneously exploited all the LIRs in the multiparameter temperature readings and found a relative sensitivity that was 30 times greater than that of the standard approach. Full article

Herein, we investigate the performance of single- and multiparametric luminescence thermometry founded on the temperature-dependent spectral features of Ca₆BaP₄O₁₇:Mn⁵⁺ near-infrared emission. The material was prepared by a conventional steady-state synthesis, and its photoluminescence emission was measured from 7500 to 10,000 cm⁻¹ over the 293–373 K temperature range in 5 K increments. The spectra are composed of the emissions from ¹E → ³A₂ and ³T₂ → ³A₂ electronic transitions and Stokes and anti-Stokes vibronic sidebands at 320 cm⁻¹ and 800 cm⁻¹ from the maximum of ¹E → ³A₂ emission. Upon temperature increase, the ³T₂ and Stokes bands gained in intensity while the maximum of ¹E emission band is redshifted. We introduced the procedure for the linearization and feature scaling of input variables for linear multiparametric regression. Then, we experimentally determined accuracies and precisions of the luminescence thermometry based on luminescence intensity ratios between emissions from the ¹E and ³T₂ states, between Stokes and anti-Stokes emission sidebands, and at the ¹E energy maximum. The multiparametric luminescence thermometry involving the same spectral features showed similar performance, comparable to the best single-parameter thermometry. Full article

We report the procedure for hydrothermal synthesis of ultrasmall Yb³⁺/Tm³⁺ co-doped Sr₂LaF₇ (SLF) upconversion phosphors. These phosphors were synthesized by varying the concentrations of Yb³⁺ (x = 10, 15, 20, and 25 mol%) and Tm³⁺ (y = 0.75, 1, 2, and 3 mol%) with the aim to analyze their emissions in the near IR spectral range. According to the detailed structural analysis, Yb³⁺ and Tm³⁺ occupy the La³⁺ sites in the SLF host. The addition of Yb³⁺/Tm³⁺ ions has a huge impact on the lattice constant, particle size, and PL emission properties of the synthesized SLF nanophosphor. The results show that the optimal dopant concentrations for upconversion luminescence of Yb³⁺/Tm³⁺ co-doped SLF are 20 mol% Yb³⁺ and 1 mol% Tm³⁺ with EDTA as the chelating agent. Under 980 nm light excitation, a strong upconversion emission of Tm³⁺ ions around 800 nm was achieved. In addition, the experimental photoluminescence lifetime of Tm³⁺ emission in the SLF host is reported. This study discovered that efficient near IR emission from ultrasmall Yb³⁺/Tm³⁺ co-doped SLF phosphors may have potential applications in the fields of fluorescent labels in bioimaging and security applications. Full article

The sensitivity of luminescence thermometry is enhanced at high temperatures when using a three-level luminescence intensity ratio approach with Dy³⁺- activated yttrium aluminum perovskite. This material was synthesized via the Pechini method, and the structure was verified using X-ray diffraction analysis. The average crystallite size was calculated to be around 46 nm. The morphology was examined using scanning electron microscopy, which showed agglomerates composed of densely packed, elongated spherical particles, the majority of which were 80–100 nm in size. The temperature-dependent photoluminescence emission spectra (ex = 353 nm, 300–850 K) included Dy³⁺ emissions in blue (458 nm), blue (483 nm), and violet (430 nm, T 600 K). Luminescence intensity ratio, the most utilized temperature readout method in luminescent thermometry, was used as the testing method: a) using the intensity ratio of Dy³⁺ ions and ⁴I_15/2→⁶H_15/2/⁴F_9/2→⁶H_15/2 transitions; and b) employing the third, higher energy ⁴G_11/2 thermalized level, i.e., using the intensity ratio of ⁴G_11/2→⁶H_15/2/⁴F_9/2→⁶H_15/2 transitions, thereby showing the relative sensitivities of 0.41% K⁻¹ and 0.86% K⁻¹ at 600 K, respectively. This more than doubles the increase in sensitivity and therefore demonstrates the method’s usability at high temperatures, although the major limitation of the method is the chemical stability of the host material and the temperature at which the temperature quenching commences. Lastly, it must be noted that at 850 K, the emission intensities from the energetically higher levels were still increasing in YAP: Dy³⁺. Full article