Luminescence Lifetime Research Articles

Luminescence lifetime tuning of non-conjugated organic clusters through external heavy-atom effect for smartphone-based time-resolved imaging

Clusteroluminescence from non-conjugated organic molecules has attracted extensive attention, and it is extraordinarily important to develop effective methods for tuning the clusteroluminescence lifetime with balanced emission intensity in optical multiplexing for time-resolved luminescence imaging. Herein, chitosan, a renewable polymer, was found to exhibit persistent clusteroluminescence after dehydration. In addition, external heavy-atom effect was successfully utilized for enhancing phosphorescence intensity and regulating its phosphorescence lifetime. By adjusting the doping concentration of bromide salts in chitosan, the phosphorescence lifetime could be gradually tailored from 49 to 647 ms. The heavy atoms could promote phosphorescence transition and avoid the reduction of short-lived luminescence component, which facilitated the lifetime-multiplexed information encryption. This strategy for tuning phosphorescence lifetime could be extended to other phosphorescence materials. Moreover, smartphone-based luminescence imaging of shrimp chitin was realized by enhancing its persistent luminescence, which indicated that our method could be used for label-free luminescence imaging of chitin-containing organisms.

Mid-infrared laser operation of Er3+-doped BaF2 and (Sr,Ba)F2 crystals.

We report on the first, to our knowledge, mid-infrared laser operation of two Er3+-doped barium-containing fluorite-type crystals, BaF2 and (Sr,Ba)F2, featuring a low-phonon energy behavior. A continuous wave 4.9 at.% Er:(Sr,Ba)F2 laser generated 519 mW at 2.79 µm with a slope efficiency of 25.0% and a laser threshold of 27 mW. The vibronic and spectroscopic properties of these crystals are determined. The phonon energy of (Sr,Ba)F2 is as low as 267 cm-1. The Er3+ ions in this crystal feature a broadband emission owing to the 4I11/2 → 4I13/2 transition and a long luminescence lifetime of the 4I11/2 level (10.6 ms) making this compound promising for low-threshold, broadly tunable, and pulsed 2.8-µm lasers.

Cancer bioimaging using dual mode luminescence of graphene/FA-ZnO nanocomposite based on novel green technique

Graphene based nanomaterials are explored in the field of cancer bioimaging and biomedical science and engineering. The luminescent nanostructures with a low toxicity and high photostability can be used as probes in bioimaging applications. This work is aimed to prepare graphene/folic acid-zinc oxide (GN/FA-ZnO) nanocomposite with dual-mode emissions (down-conversion and up-conversion) to be used in cancer bioimaging. The dual mode emissions offer long luminescence lifetime, multicolor emissions detected by the naked eyes after excitation and narrow band absorption and emission spectra. ZnO nanospheres and nanorods structures were prepared using co-precipitation technique and were conjugated with FA to separate the bulk graphite layers electrostatically into GN. The optical, morphological, surface charge and structural properties of the prepared nanostructures were investigated and discussed using different characterization techniques such as UV–visible spectroscopy, photoluminescence (PL) spectroscopy, scanning electron microscope (SEM), high resolution transmission electron microscope (HRTEM), Zeta potential, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), and Fourier transform infrared (FTIR). GN/FA-ZnO nanocomposites were injected into Swiss albino mice implanted with Ehrlich Tumor and the bioimaging was investigated using photon imager and digital camera. The results showed clear fluorescence and confirmed that the green design of GN/FA-ZnO nanocomposite with targeting behavior was capable of selective bioimaging of the tumor. This study presented a novel dual mode emission nanocomposite for tumor targeting and is a promising strategy for the fabrication of a new design of spectral encoding.

A tetraiodomanganate(II) compound with P,P'-diprotonated bis(2-diphenylphosphinophenyl)ether manifesting unexpected short luminescence lifetime

An organic–inorganic cation–anion manganese(II) tetraiodide compound with P,P'-diprotonated bis(2-diphenylphosphinophenyl)ether, [H2DPEphos][MnI4], has been synthesized and investigated. The compound has a few possible pathways for proton transfers which play an important role in the observed luminescence. The proton transfers result in the appearance of two-band luminescence and facilitate the charge transfer from organic cation to the manganese(II) ion. These bands correspond to the d-d transitions of manganese(II) and are coupled through {[H2DPEphos]}-{[MnI4]} vibrations. This leads to the averaging of the luminescence lifetimes for both band and the unexpected short observed luminescence lifetime. The reason for the two-band luminescence was additionally considered using the DFT calculations.

Two near-infrared phosphorescent iridium(III) complexes for the detection of GSH and photodynamic therapy.

GSH is one of the most important reducing agents in biological systems. The depletion of GSH in the human body is linked to many diseases. Therefore, it is necessary to develop suitable and efficient probes for detecting GSH concentrations in real samples. In this work, we designed and synthesized two near-infrared emitting iridium(III) complex probes containing a novel ligand functionalized with an α,β-unsaturated ketone for the rapid and sensitive detection of GSH. The molecular structure of Ir2 was determined by X-ray crystallography. Due to their large Stokes shift, long luminescence lifetime and NIR emission, these probes were successfully applied in the imaging of GSH in living cells. In addition, two iridium(III) complexes have strong singlet oxygen generation ability which can be used for photodynamic therapy (PDT) upon visible light irradiation. On the basis of these findings, our iridium(III) complexes may serve as GSH probes for HeLa cell imaging and as photosensitizers for PDT.

Circularly polarized luminescence and performance modulation of chiral europium-titanium (Eu2Ti4)-oxo clusters.

The designed synthesis of chiral luminescent molecules with excellent circularly polarized luminescence (CPL) performance and high quantum yield (QY) levels has attracted great interest but remains very challenging. Herein, we report three pairs of chiral europium-titanium-oxo clusters featuring both modest CPL characteristics and high QY levels (up to 79%), which can be regulated by switching between different ligand substituents.

Deep-red-emitting phosphors of Mn4+-activated tantalite for high-sensitivity lifetime thermometry and security films.

Herein, single monoclinic phase Mn4+-doped Sr2InTaO6 (SITO) phosphors were reported in terms of both luminescence behaviors and potential applications. The optimal Mn4+-doped SITO (0.3 mol%) exhibited a good color purity of 92.9% in a deep-red region with achromaticity coordinate of (0.707, 0.293). In addition, the local structure of Mn4+ in the SITO matrix was determined. The crystal-field strength was calculated to be approximately 1781.7 cm-1 whereas the nephelauxetic ratio was determined to be 1.04. Furthermore, the flexible SITO:Mn4+-YAG:Ce3+ security film was fabricated for use in anti-counterfeiting applications, which could emit different colors under various lighting sources. The SITO:Mn4+ phosphors exhibited a high sensing sensitivity based on the luminescence lifetime. Consequently, the SITO:Mn4+ phosphors can be employed in bifunctional platforms of luminescence lifetime thermometry and anti-counterfeiting applications.

Temperature dependence of radiative and non-radiative decay in the luminescence of one-dimensional pyridinium lead halide hybrids.

The photoluminescence properties of organic-inorganic pyridinium lead bromide [(pyH)PbBr3] and iodide [(pyH)PbI3] compounds were investigated as a function of temperature. The inorganic substructure consists of face-sharing chains of PbX6 octahedra. Diffuse reflectance spectra of the compounds show low energy absorption features consistent with charge transfer transitions from the PbX3 chains to the pyridinium cations. Both compounds display extremely weak luminescence at room temperature that becomes strongly enhanced upon cooling to 77 K. Broad, featureless low energy emission (λem > 600 nm) in both compounds have large Stokes shifts [1.1 eV for (pyH)PbBr3 and 0.46 eV for (pyH)PbI3] and are assigned to transitions from self-trapped excitons on the inorganic chains whereas emission at higher energy in (pyH)PbBr3 (λem = 450 nm) is assigned to luminescence from a free exciton state. Analysis of data from temperature-dependent luminescence intensity measurements gives activation energies (Ea) for non-radiative decay of the self-trapped excitons in (pyH)PbBr3 and (pyH)PbI3, (Ea = 0.077 eV and 0.103 eV, respectively) and for the free exciton in (pyH)PbBr3 (Ea = 0.010 eV). Analysis of temperature dependent luminescence lifetime data indicates another non-radiative decay process in (pyH)PbI3 at higher temperatures (Ea = 0.17 eV). A large increase in the luminescence lifetime of (pyH)PbI3 below 80 K is consistent with thermalization between triplet sublevels. Analysis of the luminescence power dependence for (pyH)PbI3 shows superlinear response suggestive of quenching by static traps.

Selective naked-eye detection of dopamine using an imino-boron molecular capsule

A BF2-containing molecular capsule with intense luminescence and long lifetimes is synthesised. The cylindrical cavity in the capsule encapsulates dopamine with the aid of multiple hydrogen bonds, leading to visual changes in colour and fluorescence.

Bipyridil-based chelators for Gd(III) complexation: kinetic, structural and relaxation properties.

In the last 20 years, research in the field of MRI (magnetic resonance imaging) contrast agents (CAs) has been intensified due to the emergence of a disease called nephrogenic systemic fibrosis (NSF). NSF has been linked to the in vivo dissociation of certain Gd(III)-based compounds applied in MRI as CAs. To prevent the dechelation of the probes after intravenous injection, the improvement of their in vivo stability is highly desired. The inertness of the Gd(III) chelates can be increased through the rigidification of the ligand structure. One of the potential ligands is (2,2',2'',2'''-(([2,2'-bipyridine]-6,6'-diylbis(methylene))bis(azanetriyl))tetraacetic acid) (H4DIPTA), which has been successfully used as a fluorescent probe for lanthanides; however, it has never been considered as a potential chelator for Gd(III) ions. In this paper, we report the thermodynamic, kinetic and structural features of the complex formed between Gd(III) and DIPTA. Since the solubility of the [Gd(DIPTA)]- chelate is very low under acidic conditions, hampering its thermodynamic characterization, we can only assume that its stability is close to that determined for the structural analogue [Gd(FENTA)]- (H4FENTA: (1,10-phenanthroline-2,9-diyl)bis(methyliminodiacetic acid)), which is similar to that determined for the agent [Gd(DTPA)]2- routinely used in clinical practice. Unfortunately, the inertness of [Gd(DIPTA)]- is significantly lower (t1/2 = 1.34 h) than that observed for [Gd(EGTA)]- and [Gd(DTPA)]2- as a result of its spontaneous dissociation pathway during dechelation. The relaxivity values of [Gd(DIPTA)]- are comparable with those of [Gd(FENTA)]- and somewhat higher than the values characterizing [Gd(DTPA)]2-. Luminescence lifetime measurements indicate the presence of one water molecule (q = 1) in the inner sphere of the complex with a relatively high water exchange rate (k298ex = 43(5) × 106 s-1). DFT calculations suggest a rigid distorted tricapped trigonal prismatic polyhedron for the Gd(III) complex. On the basis of these results, we can conclude that the bipyridine backbone is not favourable with respect to the inertness of the chelate.

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.

ZnGa2-xAlxO4 (x = 0 ≤ 2) spinel for persistent light emission and HER/OER bi-functional catalysis.

Spinel materials have demonstrated diverse applications in various fields, especially in the energy sector. Since the pure spinel structure has the limitations of poor inherent activity and low conductivity, defect engineering through octahedral B-site modulation is expected to enhance various properties. Here in this work, we have synthesized ZnGa2-xAlxO4 (x = 0 ≤ 2) spinel and moved from one terminal (ZnGa2O4) to the other (ZnAl2O4) by varying the Ga/Al ratio using solvent-free solid-state reaction. Dopant and rare earth element-free (RE) ZnGa2O4 spinel showed excellent blue luminescence with photoluminescent quantum yields (PLQY) of 13% while exhibiting persistent light emission close to 60 min. The Al3+ incorporation at Ga3+ site doesn't yield any improvement in persistent luminescence lifetime owing to quenching of shallow traps as suggested by thermoluminescence (TL) studies. Moreover our materials have demonstrated bifunctional electrocatalytic activity towards both oxygen evolution (OER) and hydrogen evolution reaction (HER) which has never been reported for ZnGa2-xAlxO4. X-ray photoelectron spectroscopy (XPS) and positron annihilation lifetime spectroscopy (PALS) suggested that mixed Al/Ga-containing spinels possessed enhanced oxygen vacancies/defects. This makes them better electrocatalyst towards OER and HER compare to ZnGa2O4 and ZnAl2O4. The ZnGa1.75Al0.25O4 composition by virtue of enhanced oxygen vacancies and less charge transfer resistance (47.3 ohms) demonstrated best electrocatalytic activity for OER compared to the other synthesized catalysts at the same applied potential (1.6 V). On the other hand, the ZnGa1Al1O4 composition demonstrated excellent faradaic efficiency of ∼ 90% towards HER. From this work we can achieve multifunctional applications towards optoelectronics and electrocatalysis just by modulating Al/Ga ratio in ZnGa2-xAlxO4.

U-type π-conjugated phosphorescent ligand sensitized lanthanide metal-organic frameworks for efficient white-light-emitting diodes.

Lanthanide metal-organic framework (Ln-MOF) based phosphors for light-emitting diodes (LEDs) play an important role in the fields of solid-state lighting and display. The rational design of organic antennae to address the drawback of low extinction coefficients of the lanthanide ions is highly desired. In this work, we provide a new design strategy to achieve an energy transfer molecule with a through-space conjugated folded structure, which can strengthen the skeleton rigidity and facilitate triplet state energy transfer. Consequently, one U-type π-conjugated molecule 2,6-bis(3,5-dicarboxylphenoxy) pyridine (H4L) was selected as a light gatherer to sensitize lanthanide ions for the construction of Ln-MOFs [Ln(HL)(H2O)3]n (Eu-MOF and Tb-MOF), which exhibit a long-lived luminescence lifetime (0.88 ms for Eu-MOF and 1.31 ms for Tb-MOF) and high quantum yields (50.87% for Eu-MOF and 85.64% for Tb-MOF). Furthermore, a white LED device with a colour rendering index (89) was fabricated using the mixture of Ln-MOFs with a commercial blue phosphor.

Thermally activated delayed fluorescence in a deep red dinuclear iridium(iii) complex: a hidden mechanism for short luminescence lifetimes

Thermally activated delayed fluorescence (TADF) is found to play an important role in accelerating the rate of radiative decay in luminescent iridium(iii) complexes, shown in this instance for dinuclear complexes formed with high stereoselectivity.

Спектральные и люминесцентные свойства Yb-=SUP=-3+-=/SUP=- в растворах CCl_4-GaCl_3-Yb-=SUP=-3+-=/SUP=-

The absorption and luminescence spectra and the luminescence lifetime of the excited state 2F5/2 of Yb3+ ions in CCl4 – GaCl3 – Yb3+ solutions have been measured. Information was obtained on the Stark splitting of levels, on the absorption and stimulated emission cross sections, and on the quantum yield of Yb3+ luminescence. The spectral dependences of the gain cross section are calculated for different relative inverse populations of the 2F5/2 excited state. Based on an analysis of the spectral and laser properties of Yb3+, it was concluded that the use of CCl4 – GaCl3 – Yb3+ solutions as the active medium of a liquid ytterbium laser is promising. Keywords: carbon tetrachloride, ytterbium, absorption, luminescence, lifetimes, Stark splitting, gain cross section

Protein charge transfer spectra in a monomeric protein with no lysine.

UV-Visible absorption and luminescence originating from non-aromatic groups in proteins is being intensely investigated today. Earlier work has shown that non-aromatic charge clusters in a folded monomeric protein can collectively act like a chromophore. Incident light in the near UV-Visible wavelength causes photoinduced electron transfer from the Highest Occupied Molecular Orbital (HOMO) of the electron-rich donor (like a carboxylate anion) to the Lowest Unoccupied Molecular Orbital (LUMO) of the electron-deficient acceptor (like a protonated amine or the polypeptide backbone) in the protein giving rise to absorption spectra in the 250-800 nm range referred to as Protein Charge Transfer Spectra (ProCharTS). The transferred electron can relax back from the LUMO to fill up the hole in the HOMO by a charge recombination process, emitting weak ProCharTS luminescence. Previous studies in monomeric proteins displaying ProCharTS absorption/luminescence always involved lysine-containing proteins. The lysine (Lys) sidechain plays a dominant role in ProCharTS; however, experimental evidence for ProCharTS among proteins/peptides devoid of Lys is lacking. Recently, the absorption features of charged amino acids have been examined using time-dependent density functional theory calculations. In this study, we show that amino acids: arginine (Arg), histidine (His) and aspartate (Asp); homo-polypeptides: poly-arginine and poly-aspartate; and a protein: Symfoil PV2 that is rich in Asp, His and Arg, but lacks Lys, profusely display ProCharTS. The folded Symfoil PV2 protein displayed maximum ProCharTS absorptivity in the near UV-Vis region, in comparison to the homo-polypeptides and amino acids. Furthermore, features like overlapping ProCharTS absorption spectra, decreasing ProCharTS luminescence intensity with longer excitation wavelength, large Stokes shift, multiple excitation bands and multiple luminescence lifetime components appeared to be conserved across peptides, proteins and amino acids studied. Our results underscore the utility of ProCharTS as an intrinsic spectral probe to monitor the structure of any protein that is rich in charged amino acids.

Structure and luminescence properties of Dy3+ doped quaternary tungstate Li3Ba2Gd3(WO4)8 for application in wLEDs.

Quaternary tungstates with the composition Li3Ba2Gd3(WO4)8 doped with different concentrations of Dy3+ (from 0.5 to 10 at%) were prepared by the solid-state reaction method at 900 °C. Their structural, spectroscopic and optical properties were studied systematically in this work. X-ray diffraction analysis confirmed the crystallization of Li3Ba2Gd3(WO4)8 to have a monoclinic structure (sp. gr. C2/c); the lattice constants for 1 at% doping concentration of Dy3+ are a = 5.2126(2) Å, b = 12.7382(1) Å, c = 19.1884(3) Å, Vcalc = 1273,40(4) Å3 and β = a × c = 91.890(9)°. The first principles calculations for the undoped crystal revealed a direct bandgap of 2.45 eV, which is very close to the experimental one. The identified broad, and strong excitation peak at 450 nm indicates that Li3Ba2Gd3(WO4)8:Dy3+ phosphors are suitable to be pumped by a blue laser diode (LD). Under excitation at 445 nm, the phosphor showed a stronger luminescence peak at 575 nm which corresponds to the Dy3+:4F9/2 → 6H13/2 transition, and three weaker emissions peaks at 477, 661, and 750 nm. Meanwhile, the effect of different Dy3+ contents on the luminescence properties was investigated. The optimum concentration to minimize the quenching effect was 4 at% and the critical distance is 31.209 Å. The phosphor emitted strong greenish-yellow light situated at (0.425, 0.472) in CIE coordinates with a color temperature of 3652 K. All the measured luminescence lifetime curves exhibited a single-exponential nature. Excellent thermal stability was found for this tungstate phosphor (the activation energy is 0.352 ± 0.01 eV). The measured absolute photoluminescence quantum yield was around 10.5%. The results presented in this work show that Li3Ba2Gd3(WO4)8:Dy3+ phosphors with strong yellow emission are promising candidates for white-light emitting LED (wLED) applications.

Polarized spectroscopy of Sm3+ ions in monoclinic KGd(WO4)2 crystals

We report on a polarization-resolved spectroscopic study of Sm3+-doped monoclinic KGd(WO4)2 crystals. The transition probabilities for Sm3+ ions were calculated using a modified Judd-Ofelt theory. For the 4G5/2 → 6H9/2 transition in the red spectral range, the stimulated-emission cross-section is 5.59×10-21 cm² at 649.0 nm (for light polarization E || Np) and the luminescence lifetime of the 4G5/2 state is 719 μs (0.4 at.% Sm3+-doping). Sm:KGd(WO4)2 is promising for orange and red lasers.

Deep learning enhanced NIR-II volumetric imaging of whole mice vasculature

Fluorescence imaging through the second near-infrared window (NIR-II,1000–1700 nm) allows in-depth imaging. However, current imaging systems use wide-field illumination and can only provide low-contrast 2D information, without depth resolution. Here, we systematically apply a light-sheet illumination, a time-gated detection, and a deep-learning algorithm to yield high-contrast high-resolution volumetric images. To achieve a large FoV (field of view) and minimize the scattering effect, we generate a light sheet as thin as 100.5 μm with a Rayleigh length of 8 mm to yield an axial resolution of 220 µm. To further suppress the background, we time-gate to only detect long lifetime luminescence achieving a high contrast of up to 0.45 <italic>Ι</italic>_contrast. To enhance the resolution, we develop an algorithm based on profile protrusions detection and a deep neural network and distinguish vasculature from a low-contrast area of 0.07 <italic>Ι</italic>_contrast to resolve the 100 μm small vessels. The system can rapidly scan a volume of view of 75 × 55 × 20 mm³ and collect 750 images within 6 mins. By adding a scattering-based modality to acquire the 3D surface profile of the mice skin, we reveal the whole volumetric vasculature network with clear depth resolution within more than 1 mm from the skin. High-contrast large-scale 3D animal imaging helps us expand a new dimension in NIR-II imaging.

Plasmon effect on triplet-singlet energy transfer in the dye-doped Langmuir-Blodgett films

The effect of silver plasmonic nanoparticles on triplet-singlet energy transfer in the donor-acceptor pair of organic dyes was studied. Layered dye films were prepared on the surface of glass and island silver films using the Langmuir-Blodgett method. Amphiphilic analogs of Rose bengal and polymethine dye were used as donor and acceptor of energy. A polymer monolayer was deposited between monolayers of donor and acceptor molecules to exclude the competing triplet-triplet energy transfer. The spectra of delayed fluorescence and phosphorescence of donor-acceptor films and the delayed luminescence lifetime of donor in these films have been measured. It is shown that a threefold increase in the fluorescence intensity and a twofold increase in the donor phosphorescence intensity are observed on silver island films. The successful triplet-singlet energy transfer is evidenced by both the quenching of donor centers and appearance of sensitized delayed fluorescence of the acceptor with the duration close to the donor triplet lifetime. In the presence of silver nanoparticles, in addition to enhancement in the intensity of the donor emission, an increase in the efficiency of tripletsinglet energy transfer was observed. The obtained results can be used in various optical devices.