Luminescence Kinetics Research Articles

Investigating the Potential of Cr3+-Doped Pyroxene for Highly Sensitive Optical Pressure Sensing.

Luminescent manometry has gained significant popularity in recent years due to its capability to provide in situ pressure measurements in a remote manner. Therefore, there is a growing need to identify phosphors with pressure-dependent spectroscopic properties that can be utilized to develop highly sensitive pressure sensors operating over a wide pressure range. Hence, we present a novel temperature-invariant luminescent manometer based on Cr3+ ion emission in pyroxene Ca0.8Sr0.2MgSi2O6:Cr3+. We utilized two readout modes, including an innovative luminescent pressure sensing ratiometric approach based on the broad emission band associated with the 4T2g → 4A2g electronic transition of Cr3+ ions. This approach provided an exceptionally high sensitivity of SR = 50.7 ± 0.5% GPa-1 and ensured temperature-independent pressure measurements, thus offering highly reliable readouts. Furthermore, the proposed readout mode, which leverages changes in luminescence kinetics, demonstrated high sensitivity at high pressure at around 5 GPa (SR ∼ 8 ± 0.2% GPa-1) surpassing the performance of luminescence kinetics-based manometers reported to date. Consequently, Ca0.8Sr0.2MgSi2O6:Cr3+ emerges as a highly promising phosphor with significant application potential for pressure sensing across a broad pressure range.

Sub-∘C-precision temperature imaging using phase-shift luminescence thermometry

Abstract This work explores the potential of luminescence thermometry to provide temperature imaging with high temperature resolution using the phase-shift method. Phosphor thermometry has been widely used for temperature imaging, especially with the decay-time method. However, the phase-shift method was rarely used. In this approach, excitation is modulated in time, and due to the temperature-dependent luminescence dynamics of the painted luminescent probe, the emission waveform is phase-shifted with respect to the excitation waveform. Initially, a parametric study was performed on the effect of excitation waveform frequency and shape, based on a millisecond-decay time phosphor. The study found that the best precision is achieved with a square waveform at a frequency such that the phase shift is π 4 at the target temperature. Then, this method was compared with the well-established decay-time method. Phase-shift method offered a three-fold improvement in temperature precision under identical peak excitation power. Finally, two-dimensional measurements were demonstrated on a temperature-controlled plate using a high speed CMOS camera, and an LED illumination. A temperature precision of 0.13 ∘C was obtained at a temporal resolution of 0.25 s and a spatial resolution of around 1 mm, due to a pre-processing binning of 7 by 7 pixels. This technique can be used as a robust alternative to infrared thermometry to probe the thermal processes with small temperature differences.

Temperature Changes in Luminescence of Mixed Complexes of Terbium and Samarium with Organic Ligands Based on 2,2-bipyridyldicarboxamides

Solutions in acetonitrile of three mixed complexes of rare earth elements (terbium and samarium) with organic ligands with various pyridine substituents were studied in this work. The ratios of ligands and metals in the resulting complexes were determined, and the stability constants of samarium complexes were calculated using the spectrophotometric titration method. Measurements of absorption, emission and excitation spectra of luminescence, luminescence kinetics of solutions of mixed complexes of rare earth elements with an excess of metal relative to the ligand were carried out at various temperatures in the range 298–328 K. An increase of luminescence intensity of a samarium ion in complex upon heating has been discovered for the first time. The dependences of the luminescence quantum yield and lifetime of mixed complexes on temperature were obtained. A thermometric parameter — the ratio of the integral luminescence intensities of samarium and terbium ions — was proposed, and the temperature sensitivity coefficient of this parameter was determined for different complexes.

Exploration and Determination Strategy of the Applicable Scope of Upconversion Luminescence Dynamics Models

Exploration and Determination Strategy of the Applicable Scope of Upconversion Luminescence Dynamics Models

Growth, Spectroscopic Characterization and Continuous-Wave Laser Operation of Er,Yb:GdMgB5O10Crystal

A transparent Er3+,Yb3+:GdMgB5O10 single crystal with dimensions up to 24 × 15 × 12 mm was grown successfully by the high-temperature solution growth on dipped seeds technique from K2Mo3O10-based solvent. The grown crystal was characterized using PXRD, DSC and ATR techniques. Differential scanning calorimetry measurements and SEM analysis of the heat-treated solids revealed Er,Yb:GdMgB5O10 to be an incongruent melting compound with an onset point of 1087 °C. The absorption edge of the Er,Yb:GMBO sample is located in the region of 245 nm, which approximates a value of 4.8 eV. Absorption and emission spectra, and luminescence kinetics, were studied. The energy transfer efficiency from ytterbium to erbium ions was determined. The laser operation in continuous-wave mode was realized and output characteristics were measured. The maximal output power of 0.15 W with a slope efficiency of 11% was obtained at 1568 nm.

Impact of high sensitizer doping on the transient multiband upconversion luminescence in β-NaYF4:Yb/Ho microcrystals

Under intense near-infrared light excitation, upconversion luminescence (UCL) nanomaterials exhibit multiband emission and high sensitizer quenching concentration, indicating the potential to enhance upconversion (UC) quantum efficiency. In comparison to other common activator ions (e.g. Er3+, Tm3+, Ho3+), Ho3+ possesses abundant energy levels. However, previous studies mostly focused on the red (Ho3+:5F5 → 5I8) and green (Ho3+:5F4,5S2 → 5I8) emissions. In this paper, we have examined the transient UCL characteristics of β-NaYF4:Yb/Ho microcrystals (MCs) excited by a high-power 976 nm ns pulsed laser (∼0.32 GW/cm2). The energy transfer (ET) pathways with varying Yb3+ doping (20–98 mol%) are determined by the time evolution spectra. In high Yb3+ doping system (98 mol%), the electron population of Ho3+ accelerates, and the multiband UC rise is shortened by 6 times (from ∼3 μs to ∼500 ns). We identified a new pathway for electron populating with higher Yb3+ doping ( ≥ 40 mol%), which is Yb3+:2F5/2 + Ho3+:3L9 → Yb3+:2F7/2 + Ho3+:3M9. As Yb3+ concentration increases, the varying lifetime and intensity distribution of UCL leads to variations in the luminescence color evolution. Our result shows that altering the Yb3+ doping concentration provides a way to control the energy flow between energy levels of Ho3+, which can modulate the rise time and color evolution of Yb–Ho co-doped UC MCs. This study is expected to promote the advancement of fast-respond optoelectronic devices, UC displays, and micro-nano lasers. Kewordsmultiband upconversion luminescence; high-power excitation; upconversion luminescence dynamics; high sensitizer concentration; upconversion pathways.

Efficient and Tunable Near-Infrared Luminescence in Cubic Phosphate K2AlTi(PO4)3:Cr3+ for Spectroscopy Applications.

Broadband near-infrared (NIR) phosphors are crucial components of NIR phosphor-converted light-emitting diode (pc-LED) sources for various smart spectroscopy applications. However, developing an efficient, tunable, and inexpensive broadband NIR phosphor with sufficient spectral coverage remains a great challenge. In this work, a cubic phosphate K2AlTi(PO4)3 with highly structural rigidity was chosen as host material for Cr3+ substitution to create an efficient NIR emission. Synthesizing this compound, the obtained material exhibits a broadband NIR emission covering 700-1200 nm with a peak wavelength ranging from 820 to 860 nm depending on the Cr3+ substituting concentration. The Cr3+ concentration optimized sample possesses a photoluminescence quantum yield (PLQY) of 76.4% with an emission peak centered at 857 nm and a full width at half-maximum (fwhm) of 184 nm under 464 nm exaction, demonstrating an efficient and relatively long-wavelength NIR emission with wide spectral coverage. This broadband NIR emission is mainly derived from a single kind of emission center deduced from spectral analysis, luminescence dynamics, and first-principle calculations. Using this material, the fabricated NIR pc-LED device presents an excellent NIR output power and NIR photoelectric conversion efficiency, making this material attractive in practical applications of night-vision and bioimaging. Therefore, this work not only provides a broadband NIR material with superiorities of low cost, high efficiency, wide-range tunability, wide spectral coverage, and relatively long-wavelength NIR emission for spectroscopy applications but also highlights some clues to discover this kind of materials.

Size‐Dependent Optical Properties and Exciton Self‐Trapping Emission in Carbon Quantum Dots

AbstractCarbon quantum dots (CQDs), synthesized through controlled microplasma treatment of orange juice, exhibit unique luminescent characteristics. The impact of synthesis time on particle size was investigated. Deconvoluted emission spectra displayed broad bands, peaking at an excitation wavelength of 350 nm for CQD sizes of 2.06, 2.4, and 3.09 nm, indicating multiple fluorescence peaks. This suggests a mixture of CQDs with different excitation energies on their surfaces. Luminescence kinetics unveiled three exponential decay components with time constants of 2.73, 4.61, and 3.27 ns, indicating multiple luminescent centers. Emission behavior affected by excitation wavelengths ranging from 350 to 490 nm suggests that quantum transition probabilities are influenced by impurities or defects. These findings emphasize the size‐dependent optical properties and exciton self‐trapping (EST) emission of CQDs. The calculation of the Huang‐Rhys factor S values underscores the profound influence of carrier‐phonon coupling and the Huang‐Rhys factor on the emergence of ESTs within CQDs. Understanding these interactions is crucial for fully utilizing the capabilities of CQDs in applications spanning optoelectronics, sensors, bioimaging, and various technological fields.

Iron protoporphyrin IX-hyaluronan hydrogel-supported luminol chemiluminescence for the detection of nitric oxide in physiological solutions

Due to its role as a free radical signal-transducing agent with a short lifespan, precise measurement of nitric oxide (●NO) levels presents significant challenges. Various analytical techniques offer distinct advantages and disadvantages for ●NO detection. This research aims to simplify the detection process by developing a hydrogel system using iron(III)-protoporphyrin IX (hemin)-loaded hyaluronan for the detection of ●NO in solution. Various hydrogel formulations were created, and the effects of their components on hydrogel-supported luminol chemiluminescence (CL) kinetics, radical scavenging, and physicochemical properties were analysed through factorial analysis. The candidate formulations were then evaluated using two ●NO donors. An increase in the degree of crosslinking in unloaded formulations enhanced interactions with the CL reaction components, hydrogen peroxide (H2O2) and luminol, thereby affecting light generation. However, hemin loading negated these effects, resulting in more prominent luminescence kinetics in formulations with lower crosslinking degrees. Similarly, ●NO influenced the kinetics differently, interacting with both the CL reaction and hydrogel components. Hemin-loaded formulations exhibited enhanced signal propagation when exposed to ●NO, followed by H2O2 and luminol, whereas reversing the order of addition inhibited this propagation. The magnitude of these luminescence changes depended on the type and concentration of the ●NO donor, demonstrating greater sensitivity to ●NO levels compared to amperometric sensing. These findings suggest that the studied hydrogel platform has potential for the facile and accurate detection of ●NO in solution, requiring minimal sample sizes.

Equal Rights for Activators – Ytterbium to Terbium Cooperative Sensitization in Molecular Upconversion

AbstractMolecular scaffolds are ideal for investigating upconversion (UC) at the highest spatial resolution and to create precisely controllable luminescent materials. Such control may be the key to overcoming the limitations of brightness and reproducibility found in UC micro‐ and nanoparticles. Cooperative UC can significantly increase luminescence brightness and bulk studies showed that highest efficiencies can be obtained by sensitizer‐to‐activator ion ratios ≥ 2, that is, via high probabilities of sensitizing the emitting lanthanide ion. Using nonanuclear molecular complexes, the authors demonstrate both experimentally and theoretically that interion distances are more relevant and that the highest UC efficiencies are actually attained for sensitizer‐to‐activator ion ratios around 1. By modeling accretive and cooperative sensitization UC, energy migration, and fitting experimental data, it is revealed that cooperative sensitization is predominant for the determination of UC luminescence intensities, whereas energy migration defines UC luminescence kinetics. The implementation of interion distances and different energy transfer mechanisms into advanced modeling of experimental UC data will be paramount for designing brighter and better UC materials.

Luminescence Dynamics of BaAl2O4:Eu2+ Phosphor.

We studied steady-state and time-resolved photoluminescence of Eu doped BaAl2O4 phosphor. The undoped BaAl2O4 sample shows a dominant blue emission band at ~ 428nm and two secondary maxima at ~ 405 and 456nm due to F-centre and aggregate defects such as F2 -centre. The samples after doping of Eu at 1-5% show additional emission bands at ~ 485 and 518 nm due to Eu2+ centre and a red emission band at ~ 657nm is attributed to Eu3+ centre. The sample doped with 2% of Eu shows anomalous emission having the dominant peak at ~ 494nm. The average luminescence lifetime of the emission band at ~ 428nm in the undoped sample was estimated to be (3.29 ± 0.91) ns. The average luminescence lifetime of this emission band after doping of Eu was found to increase by 102 orders of magnitude. The intensity of the 428nm blue emission band was found to quench after doping of Eu beyond 3%. The concentration quenching effect was attributed to dipole-quadrupole interaction. Further, a non-radiative fluorescence energy transfer mechanism from an extrinsic Eu2+ centre to an intrinsic F-centre is proposed to describe the luminescence dynamics of the samples.

Polarized spectroscopy of Sm3+ ions in monoclinic KGd(WO4)2 crystals for lasers emitting in the red

Single-crystals of potassium gadolinium double tungstate KGd(WO4)2 doped with Sm3+ ions up to 20 at.% were grown from the flux using K2W2O7 as a solvent and a detailed polarization-resolved spectroscopic study of Sm3+ ions was performed with the goal of developing novel materials emitting in the visible spectral range. Polarized absorption spectra were measured and 4f-4f transition intensities of Sm3+ ions were calculated using a modified Judd-Ofelt theory yielding the intensity parameters of Ω2 = 8.027, Ω4 = 7.210 and Ω6 = 2.322 [10−20 cm2] and α = −0.017 [10−4 cm]. Polarized stimulated-emission properties of Sm3+ ions were studied. For the 4G5/2 → 6H9/2 transition in the red, the maximum σSE is 0.55 × 10−20 cm2 at 649.0 nm for light polarization E || Np (luminescence branching ratio: 40.2 %). The radiative lifetime of the 4G5/2 state is 734 μs. The luminescence dynamics from this manifold was analyzed using the Inokuti-Hirayama model. The possible role of 4f – 4f excited-state absorption from the 4G5/2 level in preventing laser operation in the orange and deep red is analyzed. A 0.8 at.% Sm:KGd(WO4)2 laser generated an output power of 37.8 mW at 649 nm, with a laser threshold of 87 mW and a slope efficiency of 17.6 %.

Exploring luminescence dynamics in Ce3+/Er3+ co-doped lithium zinc barium borate optical glasses: A study for advancing photonic technologies

Lithium zinc barium borate glasses were synthesized using the melt-quenching method and doped with Ce3+, Er3+, and their combination. The study examines the influence of Ce3+ on the photoluminescence of Er3+ in these glasses. X-ray diffraction confirmed the amorphous nature of both undoped and doped glasses, while Fourier-transform infrared spectroscopy showed the conversion of BO3 to BO4 units, and Raman spectroscopy indicated a phonon energy around 1136 cm−1. The Ce3+-doped glasses exhibited a blue emission at 447 nm due to the 5d→4f1 transition. Co-doping with Ce3+ and Er3+ led to decreased visible upconversion emissions but significantly enhanced near-infrared emissions at 1.53 μm. This enhancement is attributed to reduced non-radiative decay and improved energy transfer between Er3+ and Ce3+ ions, facilitated by the phonon energy of host glass. The 1.53 μm emission intensity in Ce3+/Er3+ co-doped glass was about 60% higher than in singly Er3+-doped samples, highlighting the potential of Ce3+ co-doping for broad amplification at 980 nm excitation.

Hemin as a Molecular Probe for Nitric Oxide Detection in Physiological Solutions: Experimental and Theoretical Assessment.

Given its pivotal role in modulating various pathological processes, precise measurement of nitric oxide (●NO) levels in physiological solutions is imperative. The key techniques include the ozone-based chemiluminescence (CL) reactions, amperometric ●NO sensing, and Griess assay, each with its advantages and drawbacks. In this study, a hemin/H2O2/luminol CL reaction was employed for accurately detecting ●NO in diverse solutions. We investigated how the luminescence kinetics was influenced by ●NO from two donors, nitrite and peroxynitrite, while also assessing the impact of culture medium components and reactive species quenchers. Furthermore, we experimentally and theoretically explored the mechanism of hemin oxidation responsible for the initiation of light generation. Although both hemin and ●NO enhanced the H2O2/luminol-based luminescence reactions with distinct kinetics, hemin's interference with ●NO/peroxynitrite- modulated their individual effects. Leveraging the propagated signal due to hemin, the ●NO levels in solution were estimated, observing parallel changes to those detected via amperometric detection in response to varying concentrations of the ●NO-donor. The examined reactions aid in comprehending the mechanism of ●NO/hemin/H2O2/luminol interactions and how these can be used for detecting ●NO in solution with minimal sample size demands. Moreover, the selectivity across different solutions can be improved by incorporating certain quenchers for reactive species into the reaction.

Unraveling Broadband Near-Infrared Luminescence in Cr3+-Doped Ca3Y2Ge3O12 Garnets: Insights from First-Principles Analysis.

In this study, we conducted an extensive investigation into broadband near-infrared luminescence of Cr3+-doped Ca3Y2Ge3O12 garnet, employing first-principles calculations within the density functional theory framework. Our initial focus involved determining the site occupancy of Cr3+ activator ions, which revealed a pronounced preference for the Y3+ sites over the Ca2+ and Ge4+ sites, as evidenced by the formation energy calculations. Subsequently, the geometric structures of the excited states 2E and 4T2, along with their optical transition energies relative to the ground state 4A2 in Ca3Y2Ge3O12:Cr3+, were successfully modeled using the ΔSCF method. Calculation convergence challenges were effectively addressed through the proposed fractional particle occupancy schemes. The constructed host-referred binding energy diagram provided a clear description of the luminescence kinetics process in the garnet, which explained the high quantum efficiency of emission. Furthermore, the accurate prediction of thermal excitation energy yielded insights into the thermal stability of the compound, as illustrated in the calculated configuration coordinate diagram. More importantly, all calculated data were consistently aligned with the experimental results. This research not only advances our understanding of the intricate interplay between geometric and electronic structures, optical properties, and thermal behavior in Cr3+-doped garnets but also lays the groundwork for future breakthroughs in the high-throughput design and optimization of luminescent performance and thermal stability in Cr3+-doped phosphors.

A study of strontium aluminates for all optical contactless sensing applications using smartphone interrogation

In the present paper we study the spectral and time responses of Eu and Dy doped strontium aluminates and compare the results obtained by means of a standard spectrometer and a smartphone. The advantages of each measurement tool are outlined. It is shown that smartphones equipped with simple transmission diffraction grating can efficiently be used in contactless sensing applications and as measurements tools for the study of the spectral and time dependent responses of phosphors. We also show that smartphones are up to an order of magnitude faster in measuring rise and decay time responses and allow a more detailed analysis of luminescence dynamics compared to spectrometers. A method of duty cycle scanning of the time responses is proposed to study the spectrally and time dependent luminescence structure dynamics which is related to the individual distribution of traps in the phosphors. These smartphone capabilities justify their use as affordable interrogation instruments for time-decay encoded phosphorescent sensors.

Diffusion-Dominated Luminescence Dynamics of CsPbBr3 Studied Using Cathodoluminescence and Microphotoluminescence Spectroscopy.

Time-resolved or time-correlation measurements using cathodoluminescence (CL) reveal the electronic and optical properties of semiconductors, such as their carrier lifetimes, at the nanoscale. However, halide perovskites, which are promising optoelectronic materials, exhibit significantly different decay dynamics in their CL and photoluminescence (PL). We conducted time-correlation CL measurements of CsPbBr3 using Hanbury Brown-Twiss interferometry and compared them with time-resolved PL. The measured CL decay time was on the order of subnanoseconds and was faster than PL decay at an excited carrier density of 2.1 × 1018 cm-3. Our experiment and analytical model revealed the CL dynamics induced by individual electron incidences, which are characterized by highly localized carrier generation followed by a rapid decrease in carrier density due to diffusion. This carrier diffusion can play a dominant role in the CL decay time for undoped semiconductors, in general, when the diffusion dynamics are faster than the carrier recombination.

Using Irradiation-Acquisition Interleaved Time-Integrated Imaging to Assess Delayed Luminescence and the Noise-Laden Residual Spontaneous Photon Emission of Yeast

Delayed luminescence from organisms informs oxidative stress that may be modulable by external stimulations. In the absence of external stress causing delayed luminescence, organisms may produce spontaneous ultraweak photon emission due to the residual oxygen demand. To better understand the oxidative state of an organism, it is desirable to acquire the delayed luminescence to reach the phase wherein the ultraweak photon emission resides. This, however, is challenging due to the significant difference in the order of magnitude of the photon counts between the two types of photon emission. Conventional time-gated measurement requires a high dynamic range to assess the noise-level photon emission, whereas simple long exposure can miss the kinetics of luminescence. There may be a compromise to be made between robustly acquiring the decay kinetics of the delayed luminescence and reliably acquiring the noise-laden spontaneous photon emission. We demonstrate an irradiation-acquisition interleaved time-integrated imaging approach that may enable the reliable acquisition of slow-decay delayed luminescence down to the level of ultraweak photon emission. Repetitive irradiation was interleaved with a gradually increased time of acquisition to assess the integrated time course of the post-irradiation luminescence. Such instrument configuration performed on yeast facilitated the use of time differentiation to assess the delayed luminescence down to the noise-level ultraweak photon emission at the expense of the total time of acquisition.

Time-resolved mid-infrared photoluminescence spectroscopy of an undoped InAs substrate

Time-resolved mid-infrared photoluminescence (PL) spectroscopy of an undoped InAs substrate has been achieved with wavelength upconversion and time-correlated single photon counting methods. The substrate exhibits multiple PL peaks at photon energies of around 0.415 eV, and the peak positions and intensities change as the temperature is varied from 3.7 to 80 K. The dominant PL peaks are attributed to free and donor-bound excitons and radiative recombination between electrons at the Fermi edge in the conduction band and holes in the valence band edge. The PL lifetime of the excitons is 12 ns, which is four times longer than that of GaAs. The band edge electron–hole recombination has a longer PL lifetime of 60 ns at 20 K. The unveiling of luminescence dynamics in narrow bandgap semiconductors will contribute to the development of mid-infrared light-emitting devices.

Combination of XEOL, TR-XEOL and HB-T interferometer at the TPS 23A X-ray nanoprobe for exploring quantum materials.

In this study, a combination of X-ray excited optical luminescence (XEOL), time-resolved XEOL (TR-XEOL) and the Hanbury-Brown and Twiss (HB-T) interferometer at the Taiwan Photon Source (TPS) 23A X-ray nanoprobe beamline for exploring quantum materials is demonstrated. On the basis of the excellent spatial resolution rendered using a nano-focused beam, emission distributions of artificial micro-diamonds can be obtained by XEOL maps, and featured emission peaks of a selected local area can be obtained by XEOL spectra. The hybrid bunch mode of the TPS not only provides a sufficiently high peak power density for experiments at each beamline but also permits high-quality temporal domain (∼200 ns) measurements for investigating luminescence dynamics. From TR-XEOL measurements, the decay lifetime of micro-diamonds is determined to be approximately 16 ns. Furthermore, the XEOL spectra of artificial micro-diamonds can be investigated by the HB-T interferometer to identify properties of single-photon sources. The unprecedented strategy of combining XEOL, TR-XEOL and the HB-T interferometer at the X-ray nanoprobe beamline will open new avenues with significant characterization abilities for unraveling the emission mechanisms of single-photon sources for quantum materials.