Luminescence Lifetime Research Articles

Structure-Activity Optimization of Luminescent Tb-doped LaF3 Nanoparticles.

A series of Tb-doped LaF3 nanoparticles (NPs) was prepared by systematically varying the Tb doping rate from 0 to 100%. The elemental composition was confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis, and the size, morphology, and crystal structure were determined in the solid state by transmission electron microscopy and X-ray diffractometry, while the size and ζ-potential of the NPs in solution were studied by dynamic light scattering, Taylor dispersion analysis, and laser Doppler electrophoresis. While the crystal structure appears to be hexagonal for a doping rate of up to 70%, an admixture of hexagonal and orthorhombic phases is observed for 80 and 90% Tb contents with a pure orthorhombic phase being obtained for TbF3. The spectroscopic properties of the NPs were studied for bare NPs and in the presence of dipicolinic acid as a surface-capping antenna ligand in solution. The coverage of the NPs by the ligand resulted in an increase in the luminescence lifetime of the emitting Tb centers, as a consequence of a better protection toward luminescence quenching from water molecules, as well as a large improvement in the brightness of the NPs. Taking into account the various parameters, a doping rate of 40% Tb was shown to be the best compromise for the development of such NPs for bioanalytical applications.

Blue Phosphorescent Pt(II) Compound Based on Tetradentate Carbazole/2,3'-Bipyridine Ligand and Its Application in Organic Light-Emitting Diodes.

The tetradentate ligand, merging a carbazole unit with high triplet energy and dimethoxy bipyridine, renowned for its exceptional quantum efficiency in coordination with metals like Pt, is expected to demonstrate remarkable luminescent properties. However, instances of tetradentate ligands such as bipyridine-based pyridylcarbazole derivatives remain exceptionally scarce in the current literature. In this study, we developed a tetradentate ligand based on carbazole and 2,3'-bipyridine and successfully complexed it with Pt(II) ions. This novel compound (1) serves as a sky-blue phosphorescent material for use in light-emitting diodes. Based on single-crystal X-ray analysis, compound 1 has a distorted square-planar geometry with a 5/6/6 backbone around the Pt(II) core. Bright sky-blue emissions were observed at 488 and 516 nm with photoluminescent quantum yields of 34% and a luminescent lifetime of 2.6 μs. TD-DFT calculations for 1 revealed that the electronic transition was mostly attributed to the ligand-centered (LC) charge transfer transition with a small contribution from the metal-to-ligand charge transfer transition (MLCT, ~14%). A phosphorescent organic light-emitting device was successfully fabricated using this material as a dopant, along with 3'-di(9H-carbazol-9-yl)-1,1'-biphenyl (mCBP) and 9-(3'-carbazol-9-yl-5-cyano-biphenyl-3-yl)-9H-carbazole-3-carbonitrile (CNmCBPCN) as mixed hosts. A maximum quantum efficiency of 5.2% and a current efficiency of 15.5 cd/A were obtained at a doping level of 5%.

Sensitive detection of choline and nicotine in real samples by switching upconversion luminescence.

Nicotine (3-(1-methyl-2-pyrrolidinyl)pyridine) is one of the most common addictive substances, causing the trace detection of nicotine to be very necessary. Herein, we designed and prepared a functionalized nanocomposite CS-PAA (NaYF4:19.5%Yb,0.5%Tm@NaYF4-PAA) using a simple method. The nicotine concentration was quantitatively detected through the inhibition of choline oxidase activity by nicotine and the luminescence intensity of CS-PAA being quenched by Fe3+. The mechanism of Fe3+ quenching CS-PAA emission was inferred by luminescence lifetime and UV-vis absorption spectra characterization. During the nicotine detection, both excitation (980nm) and emission (802nm) wavelengths of CS-PAA enable the avoidance of the interference of background fluorescence in complicated food objects, thus providing high selectivity and sensitivity with a linear range of 5-750ng/mL and a limit of detection of 9.3nM. The method exhibits an excellent recovery and relative standard deviation, indicating high accuracy and repeatability of the detection of nicotine.

2-W Ho:LaF3 laser intracavity pumped with a Tm:YLF laser

In this paper, we explore the laser properties of a 2.1 µm Ho:LaF3 laser intracavity pumped by a LD-pumped Tm:YLF laser. Ho:LaF3 crystals, with a doping concentration of 2%, have been verified as a novel type of laser gain material, whose luminescence lifetime of the 5I7 level was up to 25.7 ms. The Ho:LaF3 laser achieved an average output power of 2.07 W with a slope efficiency of 16.2%. The dual-wavelength output centered at 2089 nm and 2093 nm and exhibited excellent spot quality with M2x and M2y values of 1.19 and 1.23, respectively. Our results effectively demonstrate the impressive capability of Ho:LaF3 crystals for generating high-power 2.1 µm mid-infrared lasers.

PH-sensitive spontaneous decay of functionalized carbon dots in solutions.

Carbon quantum dots have become attractive in various applications, such as drug delivery, biological sensing, photocatalysis, and solar cells. Among these, pH sensing via luminescence lifetime measurements of surface-functionalized carbon dots is one application currently investigated for their long lifetime and autonomous operation. In this article, we explore the theoretical connection between excitation lifetimes and the pH value of the surrounding liquid via the protonation and deprotonation of functional groups. Example calculations applied to m-phenylenediamine, phloroglucinol, and tethered disperse blue 1 are shown by applying a separation approach treating the electronic wave function of functional groups separately from the internal electronic structure of the (large) carbon dot. The bulk of the carbon dot is treated as an environment characterized by its optical spectrum that shifts the transition rates of the functional group. A simple relationship between pH, pKa, and mixed fluorescence lifetime is derived from the transition rates of the protonated and deprotonated states. pH sensitivity improves when the difference in the transition rates is greatest between protonated and deprotonated species, with the greatest sensitivity found where the pKa is close to the pH region of interest. The introduced model can directly be extended to consider multicomponent liquids and multiple protonation states.

Efficient broadband NIR emission of Yb3+-activated double-perovskite tungstate Ba0.5MgLaWO6☆

Broad-band near-infrared (NIR) phosphors have garnered increasing attention due to the versatile applications in spectroscopy technology fields, but the choice of efficient NIR phosphors remains a challenge. Here, Yb3+-activated cubic double-perovskite tungstate Ba0.5MgLaWO6 was synthesized using a solid-state reaction method. A broadband NIR emission (800–1150 nm) is observed from the 2F5/2→2F7/2 transition of Yb3+ activators in Ba0.5MgLaWO6 under the excitation by UV and near-UV light. Photoluminescence (PL) spectra, decay and emission lifetimes, concentration-dependent intensities, and low temperature luminescence of Yb3+-activated Ba0.5MgLaWO6 were investigated to study the energy transfer (ET) from isolated WO6 polyhedra to Yb3+ activators. The main luminous mechanism involves cooperative energy transfer (CET), wherein, one high-energy excitation photon absorbed by host WO6 group converts to two NIR photons emitted by Yb3+. The partial substitution of Mo6+ for W6+ in Ba0.5MgLaWO6 further leads to a significant increase of the intensity and lifetime of the NIR luminescence. This work provides a feasible strategy for developing a new Yb3+-doped perovskite tungstate, which demonstrates efficient wavelength down-conversion from UV and near-UV to NIR. This material could find versatile applications as an effective NIR luminescent candidate.

Monometallic heteroleptic complexes of Dy(III) ion incorporating β-diketone and ancillary moieties: Photophysical and electrochemical analyses

Several luminescent ternary dysprosium complexes were synthesized and examined using diketone ligand 1,3-diphenylprop-1,3-dione (DPD) and various auxiliary ligands. Spectroscopic analysis was carried out to determine the structural and photophysical features of Dy (III) complexes. IR and proton NMR spectroscopic studies suggested the bonding of chelating moieties to the metal ion through oxygen and nitrogen atom. The optical and electronic band gap is evaluated which proposed the conducting behaviour of dysprosium complexes. Upon excitation with UV radiation, three distinct emission peaks of the Dy (III) ion are appeared at about 485 nm (J = 15/2), 575 nm (13/2) and 664 nm (11/2) corresponding to the transitions of type 4F9/2 → 6HJ. The strongest emission peak obtained at ∼ 575 nm is responsible for yellow emission of Dy (III) complexes. The yellow to blue (Y/B) ratio estimated for the transition J = 13/2 / J = 15/2 were found to be in the range of 4.19 – 2.80. The quantum yield was also determined for the Dy (III) complexes which is as: Φ1 = 0.315, Φ2 = 0.261, Φ3 = 0.183, Φ4 = 0.157. The synthesized dysprosium complexes demonstrate luminescence lifetime in decreasing order i.e. 0.600 ms > 0.510 ms > 0.431 ms > 0.323 ms. Furthermore, the chromaticity coordinates also confirm their yellow luminous behavior. These newly synthesized complexes could be utilized for developing systems significant for lighting, OLEDs and displays due to their luminous features.

Redox reactivity of LMCT and MLCT excited states of Earth‐abundant metal complexes

AbstractPrecious metal complexes, which act as excellent photoredox catalysts, have now being replaced by earth‐abundant metal complexes. This review focused on redox reactivity of ligand‐to‐metal charge transfer (LMCT) and metal‐to‐ligand charge transfer (MLCT) excited states of earth‐abundant metal complexes. Iron complexes with strongly σ‐donating NHC‐ligands (NHC = N‐heterocyclic carbene) has emerged, featuring long lived LMCT excited states due to a significantly increased barrier for deactivation via metal centered states. A Fe(III)‐NHC complex acts as an effective photoredox catalyst for various photocatalytic redox reactions. Although manganese(IV)‐oxo complexes have no long‐lived excited states (τ < < 1 ns). Once acids such as Sc(OTf)3 and HOTf are bound to the oxo moiety of Mn(IV)‐oxo complexes, the photoexcitation of acid‐bound Mn(IV)‐oxo complexes resulted in formation of the excited states with microseconds lifetimes, which are capable of oxidation of substrates including benzene to phenol. Photoexcited states of Mn(III), Mn(II) and Mn(I) complexes act as photoreductants to reduce substrates including O2. On the other hand, photoexcited states of Co(IV) and Co(III) complexes act as photooxidants, whereas those of Co(II) and Co(I) complexes act as photoreductants. With regard to the excited state lifetime, [Cr(tpe)2]3+ (tpe = 1,1,1‐tris(pyrid‐2‐yl)ethane) exhibited the longest luminescence lifetime (τ = 4500 μs), acting as an effective photoredox catalyst for photocatalytic redox reactions. The LMCT state of a Cr(0) complex acts as a super photoreductant. Thus, LMCT and MLCT excited states of earth‐abundant metal complexes are utilized as strong photooxidants and photoreductants, respectively.

Tracking Plasma Membrane Damage Using a Ruthenium(II) Complex Phosphorescent Indicator Paired with Cholesterol.

Long-term in situ plasma membrane-targeted imaging is highly significant for investigating specific biological processes and functions, especially for the imaging and tracking of apoptosis processes of cells. However, currently developed membrane probes are rarely utilized to monitor the in situ damage of the plasma membrane. Herein, a transition-metal complex phosphorescent indicator, Ru-Chol, effectively paired with cholesterol, exhibits excellent properties on staining the plasma membrane, with excellent antipermeability, good photostability, large Stokes shift, and long luminescence lifetime. In addition, Ru-Chol not only has the potential to differentiate cancerous cells from normal cells but also tracks in real time the entire progression of cisplatin-induced plasma membrane damage and cell apoptosis. Therefore, Ru-Chol can serve as an efficient tool for the monitoring of morphological and physiological changes in the plasma membrane, providing assistance for drug screening and early diagnosis and treatment of diseases, such as immunodeficiency, diabetes, cirrhosis, and tumors.

Synthesis and luminescent properties of cellulose acetate butyrate films doped with europium complex Eu(TTA)3 for optical thermometry

In this work, the luminescent β-diketonate europium complex, Eu(TTA)3, was incorporated into the polymer cellulose acetate butyrate in different concentrations in the form of composite films. The photoluminescence analysis showed that the composites improved the internal transition of the europium ion, 5D0 → 7F2, mainly responsible for the emission of red light from the complex, by providing a highly asymmetric chemical environment around the europium ion and by reducing non-radiative decays. The composite matrix also contributed to the quantum efficiency of the luminescence, reaching 38 %, by reducing the excited state deactivation rates. The luminescence lifetime of the composite linearly decayed with increasing temperature, while the luminescence intensity displayed an exponential decrease by increasing temperature, both behaviors proved to be appropriate for use in optical thermometry. The analysis of Raman spectra, Judd-Ofelt parameters, decay rates, and lifetime showed that the characteristics of the isolated complex were mostly maintained after being added to the polymeric matrix.

Ultralong luminescence lifetime imaging of edible plant tissue for humidity sensing in food packaging by a smartphone

The safety of luminescence sensors and probes used in food packaging should be seriously considered, while most luminescence sensors were artificially synthesized with unclear toxicity, and cannot be directly used as indicators that were in contact with food. To overcome this problem, a humidity indicator based on an edible plant tissue was developed without any chemical processing. We found that garlic bulbs could emit significant persistent luminescence after drying at room temperature. The luminescence lifetime decreases from hundreds of milliseconds to tens of milliseconds as humidity increases. The long-lived luminescence could easily be detected through smartphones without any sophisticated instruments. The edible garlic is expected to be used as a humidity indicator in food packaging without worrying about food safety. Furthermore, the interference of scattered light and short-lived fluorescence from foods and packages can be eliminated in time-resolved luminescence imaging, greatly increasing the signal-to-noise ratio.

Remote optical thermometry by two-dimensional LiAl5O8:Cr3+ luminescence sensor probe

Pure-phase LiAl5O8:Cr3+ leaf-like particles were synthesized by combustion synthetic route at various concentrations. Both sharp peaks and broad emission photoluminescence are apparent even at room temperature. The most optimum doping concentration of 0.75 % based on lifetime and emission intensity was chosen. Peaks of different configurations were separated by deconvolution from 120 K to 680 K, where 4T2 peak increases in temperature to the expense of the sharp 2E emissions, giving luminescence intensity ratio (LIR) relative sensitivity of 2.8 % K−1 at room temperature. Large separation between Cr3+ R lines marks their LIR as perspective at low temperatures. At high temperatures luminescence lifetime provided for 0.8 % K−1 sensitivity, while line-shift and bandwidth methods are not sensitive enough for thermometric applications. Deconvolution of peaks enabled for 10 % more precise estimation of Debye temperature (679 K).

Perovskite Quantum Dots Lasing in Double-Heterostructure through Energy Transfer.

Planar double heterostructures were initially investigated and have been successfully applied in III-V semiconductor lasers due to their excellent roles in confining both the photons and carriers. Here, we design and fabricate a (PEA)2Csn-1PbnX3n+1 (quasi-2D)/CsPbBr3 QD/quasi-2D double-heterostructure sandwiched in a 3/2 λ DBR microcavity, and then demonstrate a single-mode pure-green lasing with a threshold of 53.7 μJ/cm2 under nanosecond-pulsed optical pumping. The thresholds of these heterostructure devices decrease statistically by about 50% compared to the control group with no energy donor layers, PMMA/QD/PMMA in an identical microcavity. We show that there is efficient energy transfer from the barrier regions of the quasi-2D phases to the QD layer by transient absorption and luminescence lifetime spectra and that such energy transfer leads to marked threshold reduction. This work indicates that the double-heterostructure configurations should play a significant role in the future perovskite electrically pumped laser.

Thermosensitive chameleon films based on polystyrene doped with complexes of europium(III) and terbium(III)

New complexes of Eu(III) and Tb(III) tris(β-diketonates) with Lewis bases were synthesized. The spin-coating technique was used to produce composite films consisting of polystyrene (PS) polymer doped with mixtures of Eu(III) and Tb(III) complexes with different ratio of luminophores. An increase in the content of the Tb(III) complexes in the 5 %Eu x%Tb films intensifies emission of both the Tb3+ and Eu3+ ions due to occurring intermolecular energy transfer and leads to a significant increase in photostability of the material (the loss of luminescence intensity ratio did not exceed 0.5 %/hour). These photostable films were characterized as potential luminescent temperature sensors. The temperature sensitivity of their luminescence intensity and lifetime was investigated in the range of 298–383 K. The maximum absolute sensitivity of the films reaches 6.00 µs/K and exceeds that of all known lanthanide-containing thermal sensors designed for measuring physiological temperatures. In combination with changeable luminescence colors of the films, such a sensitivity makes these materials promising colorimetric thermal sensors for in situ temperature measurements.

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.

Thermally Enhanced Phosphorescent Carbon Nanodots for Monitoring Cold-Chain Logistics.

Room-temperature phosphorescent materials, renowned for their long luminescence lifetimes, have garnered significant attention in the field of optical materials. However, the challenges posed by thermally induced quenching have significantly hindered the advancement of luminescence efficiency and stability. In this study, thermally enhanced phosphorescent carbon nanodots (CND) are developed by incorporating them into fiber matrices. Remarkably, the phosphorescence lifetime of the thermally enhanced CND exhibits a twofold enhancement, increasing from 326 to 753ms, while the phosphorescence intensity experienced a tenfold enhancement, increasing from 25 to 245 as the temperature increased to 373K. Rigid fiber matrices can effectively suppress the non-radiative transition rate of triplet excitons, while high temperatures can desorb oxygen adsorbed on the surface of the CND, disrupting the interaction between the CND and oxygen. Consequently, a thermally enhanced phosphorescence is obtained. In addition, benefiting from the thermally enhanced phosphorescence property of CND, a warning indicator with an anti-counterfeiting function for monitoring cold-chain logistics is demonstrated based on CND.

Effect of ZnO on Luminescence Performance of Terbium-Activated Zinc Borosilicate Glasses.

In this study, terbium-doped ZnO-SiO2-B2O3-Na2O glasses were fabricated with the conventional melt-quenching method. The effect of altering the concentration of the host matrix on luminescence performance was investigated in terms of different ZnO/B2O3 and ZnO/SiO2 ratios. FT-IR results indicate that bridging oxygens (Bos) were converted to non-bridging oxygens (NBOs) with increments of ZnO. Furthermore, the emission intensity and luminescence lifetime of samples were influenced by the amount of ZnO; this was proven with photoluminescence spectra results. The maximum emission intensity was observed at a 1.1 ZnO/B2O3 ratio and a 0.8 ZnO/SiO2 ratio; however, the highest luminescence lifetime was observed at a 1.1 ZnO/SiO2 ratio. The emission intensity and luminescence lifetime of glass samples were improved by heat treatment as a result of the formation of willemite and zinc oxide phases. An increase in the ZnO/SiO2 ratio facilitated the formation of willemite and zinc oxide phases; therefore, crystallinity was directly related to the luminescence behavior of glass samples.

Luminescence and two-photon absorption assisted optical limiting properties of Ag-doped CdWO4 nanorods

The emerging demand for the fabrication of nonlinear optical materials with high limits of optical power is obvious in nonlinear optics due to their wide application in photonic devices. We report the linear and third-order nonlinear optical properties of Ag-doped CdWO4 nanorods and their dependence on Ag-doping concentration. CdWO4 nanorods with different Ag concentrations were synthesized by the chemical precipitation method and characterized by UV–Vis absorption, X-ray diffraction (XRD), Raman, Photoluminescence and its lifetime studies, X-ray Photoelectron spectroscopy and Transmission Electron Microscopy (TEM). The introduction of Ag ions has led to an increased redshift in the CdWO4 absorption spectra extended into longer wavelength bands, thus enhancing optical absorption within the visible range. The XRD pattern showed that the nanorods crystallized in a monoclinic wolframite structure. The incorporation of Ag in CdWO4 decreases the luminescence emission intensity due to surface quenching effect. Luminescence lifetime measurement reveals the longer decay lifetime for Ag-doped CdWO4 nanorods due to the reduction of density of defects and deep trap state. The nonlinear optical behaviour of the nanorods was investigated by an Open aperture Z-scan technique at 532 nm using pulsed wave Nd: YAG laser. Experimental results showed that reverse saturable absorption is responsible for the observed nonlinearity in the nanorods. The addition of Ag can significantly improve the nonlinear absorption coefficient and optical limiting effects of CdWO4 which can be used as a potential material in nonlinear optical devices.

Orange luminescence of α-Al2O3 related to clusters consisting of F centers and divalent cations.

The orange luminescence of α-Al2O3 under UV excitation is characterized by a 2.07-eV orange broadband emission that has not yet been elucidated. This emission is present in natural and synthetic crystals and powders, as well as in Be-treated samples. All orange-luminescent materials have low Fe concentration (mostly <1000 ppm) with traces of divalent cations, mostly Mg, or Be in Be-diffused material (dozens of ppm). Mg2+, Mn2+, and Be2+ cations substitute for trivalent Al. To accommodate the charge deficit, several defects are created, including oxygen vacancies also called F centers. Indeed, our excitation spectra revealed the presence of several different F centers (F, F+, and clustered F2, F2 +, F2 2+) in those samples. However, the thermal stability and the measured luminescence lifetimes do not match with previously reported characteristics of isolated F centers. Based on our experiments, we suggest that a complex aggregate of two F centers (F2 2+) trapped at divalent cations is a major cause of this uncommon microsecond lifetime emission, even if a variety of other defects, including Cr3+, V3+, or interstitial Al3+, are present.

Temperature sensing by means of a near-infrared luminescent Ca8NaBi(PO4)6F2:Nd3+ fluorapatite phosphor

Microrods of calcium sodium bismuth fluorapatite doped with neodymium, denoted as Ca8NaBi1-xNdx(PO4)6F2 (with x ranging from 0 to 0.5), were synthetized using a modified Pechini sol–gel method. The crystalline structure of these phosphors was refined using the Rietveld method and exhibited hexagonal symmetry with space group P63/m—C26h, where the lattice parameters were a = 9.3855(5) Å and c = 6.8998(6) Å for x = 0.2. The particles morphology was analyzed through SEM, revealing an average length of approximately 1.5 µm. When excited at 808 nm, the Ca8NaBi(PO4)6F2:0.2Nd3+ microrods emitted strongly at 872, 957 and 1055 nm, falling within the near-infrared region. These emissions correspond to the 4F3/2 → 4I9/2 (P2), 4F5/2 → 4I11/2(P3), 4F3/2 → 4I11/2(P1) transitions of Nd3+ ions, respectively, and are situated within the first and second biological windows. The luminescence lifetime of the 4F3/2 state of Nd3+ was measured to be 294.4 µs for the sample with the lowest Nd3+ concentration of x = 0.05. In addition, the luminescence intensity ratios P2/P1 and P3/P1 were found to be temperature dependent, potentially making it suitable for luminescent ratiometric thermal sensing. These findings suggest that the synthesized Ca8NaBi(PO4)6F2:Nd3+ microrod thermometers exhibit favorable characteristics in terms of relative sensitivity, temperature uncertainty, and repeatability within the temperature range of 303–403 K.