Emission Lifetime Research Articles

Effects of the Introduction of Tertiary Amino Linkages on the Properties of Phenothiazine Derivatives as Delayed Emission Fluorophores

AbstractTwo phenothiazine‐based electroactive compounds were synthesized by Buchwald‐Hartwig cross‐coupling reaction. The compounds consist of pyridine‐ or benzonitrile accepting moiety and phenothiazine donor fragments linked through tertiary amino linkage. The resulting electroactive compounds showed high thermal stability with 10 % weight loss temperatures of 270 and 308 °C. Both the compounds showed reversible oxidation after repeated scans of cyclic voltammetry. Experimental results in combination with the outcomes of TD‐DFT calculations, were employed to examine the emission nature of the target compounds. By demonstrating the correct choice of acceptor moiety and linking topology, the synthesized compounds were found to be emitters exhibiting efficient RTP. With emission lifetime reaching 26.04 ms and spin‐orbit coupling value of the triplet states with the singlet ground state of 18.72 cm−1, the radiative recombination of the triplet state is ensured. Having lifetimes of 26 ms and strong sensitivity to oxygen, the benzonitrile‐containing phenothiazine derivative demonstrated fast oxygen response with the quenching constant of 4.97*10−4 ppm−1 at low oxygen concentrations that is comparable to the corresponding characteristics of reported RTP‐based sensors.

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.

21‐4: The Understanding of Bottom Emission Blue OLED Efficiency, Lifetime Trends and Capacitance Curves with Different EILs

We discuss the effects of different electron injection layers (EILs) (NaF/LiF/Liq/ETL:Li) on the electrical properties, lifetime and capacitance systematically base on the bottom emission blue OLED device in the paper. We can determine the aging speed and initial decay of the OLED device from the characteristics of the capacitance. In the Addition, the mechanism of diverse inorganic electron injection layers resulting in the different characteristics of OLED devices is deeply analyzed. Finally, the cause of lifetime collapse with thicker inorganic EIL (70A) is speculatedfrom the two aspects of ion migration by TOF‐SIMS and electron injection capacity.

Efficient Blue Photo- and Electroluminescence from CF3-Decorated Cu(I) Complexes.

Luminescent organometallic complexes of earth-abundant copper(I) have long been studied in organic light-emitting diodes (OLED). Particularly, Cu(I)-based carbene-metal-amide (CMA) complexes have recently emerged as promising organometallic emitters. However, blue-emitting Cu(I) CMA complexes have been rarely reported. Here we constructed two blue-emitting Cu(I) CMA emitters, MAC*-Cu-CF3Cz and MAC*-Cu-2CF3Cz, by introducing one or two CF3 substitutes into carbazole ligands. Both complexes exhibited high thermal stability and blue emission colors. Moreover, two complexes exhibited different emission origins rooting from different donor ligands: a distinct thermally activated delayed fluorescence (TADF) from ligand-to-ligand charge transfer excited states for MAC*-Cu-CF3Cz or a dominant phosphorescence nature from local triplet excited state of the carbazole ligand for MAC*-Cu-2CF3Cz. Inspiringly, MAC*-Cu-CF3Cz had high photoluminescence quantum yields of up to 94 % and short emission lifetimes of down to 1.2 μs in doped films, accompanied by relatively high radiative rates in the 105 s-1 order. The resultant vacuum-deposited OLEDs based on MAC*-Cu-CF3Cz delivered pure-blue electroluminescence at 462 nm together with a high external quantum efficiency of 13.0 %.

Scalable fabrication of red Room-Temperature phosphorescent materials through molecular doping strategy for versatile applications

Room-temperature phosphorescence (RTP) materials renowned for their long emission lifetime have garnered tremendous research interest not only for elucidating their underlying mechanisms but also for exploring their potential applications in anti-counterfeiting, encryption, and bioimaging. Nevertheless, the RTP color of most organic materials has been limited to blue, green, and yellow. In this study, a series of red RTP materials have been successfully fabricated at a large scale through a straightforward molecular doping strategy. Remarkably, the doped materials exhibited red RTP at 622 nm and 678 nm with an ultralong lifetime of 373 ms and an efficiency of 5.21 %, which was among the best performances reported for organic RTP materials. The systematic investigation unveiled that the efficient RTP emanated from the robust interactions between the emitter and matrix molecules as well as the formation of D/A exciplexes. Furthermore, the red RTP materials could be easily manufactured into diverse forms, including fine powders, aqueous inks, and nanoparticles. Their multifunctional applications in fingerprint recognition, encryption, and live bioimaging were demonstrated. With distinctive advantages such as red RTP, ultralong lifetime, scalable production, and cost-effectiveness, these RTP materials pave the way for the extensive utilization of organic RTP materials in various engineering sectors.

226 nm Far‐Ultraviolet‐C Light Emitting Diodes with an Emission Power over 2 mW

Far‐ultraviolet‐C (far‐UVC) light emitting diodes (LED) emitting at an emission wavelength of 226 nm with different n‐AlGaN contact layers, quantum well barriers, and quantum well numbers are compared regarding their emission power, operation voltage, and lifetime. Electroluminescence measurements show higher emission power but also an increased operation voltage with increasing Al mole fraction in the n‐AlGaN contact layer. Furthermore, it is found that both the mean emission power and the device lifetime decrease with increasing Al mole fraction (82–89%) of the quantum well barriers and therefore with increasing barrier height. Finally, 226 nm LEDs with 6 and 9 quantum wells are compared. It is observed that the sample with 9 quantum wells shows an around 30% lower mean emission power but, in contrast, the L70 lifetime of these LEDs is higher by a factor of around five. Based on these optimizations, 226 nm LEDs with a maximum external quantum efficiency of 0.28% (wall plug efficiency of 0.18%) as well as an emission power of 2.1 mW and an operation voltage of 9.6 V at 200 mA are realized.

Nonlinear Optical Activity of a Chiral Organic-Inorganic ([(NH3CH2CH2)3NH])2[MnBr5]Br5 Photoluminescent and Piezoelectric Crystal.

The family of Mn-based organic-inorganic hybrids has greatly expanded due to their advantages in applications. They also show superior bright and size-tunable photoluminescence and can be considered a perfect alternative to toxic lead-based compounds. In this work, we present the detailed structural, optical, and electrical characterization of ([(NH3CH2CH2)3NH])2[MnBr5]Br5. The title compound exhibits a unique type of inorganic arrangement created by the trigonal bipyramids. It crystallizes in noncentrosymmetric space group R32, indicating its optical activity, piezoelectricity, and second-order optical nonlinearity proven by the second harmonic of light measurements. The studied crystals exhibit intense photoluminescence originating from the Mn(II) ion 4T1(G) → 6A1 transition. The measured lifetime of the photoluminescence emission is ≤1.5 ms, while the measured quantum yield for both powder and crystal samples reaches ∼70%.

Photophysical Studies of a Zr(IV) Complex with Two Pyrrolide-Based Tetradentate Schiff Base Ligands.

The reaction of two equivalents of N,N'-bis(2-pyrrolylmethylidene)-1,2-phenylenediamine (H2bppda) with tetrabenzylzirconium provided the air- and moisture-stable eight-coordinate complex Zr(bppda)2. Temperature-dependent steady-state and time-resolved emission spectroscopy established weak photoluminescence (ΦPL = 0.4% at 293 K) by a combination of prompt fluorescence and thermally activated delayed fluorescence (TADF) upon visible light excitation at and around room temperature. TADF emission is strongly quenched by 3O2 and shows highly temperature-sensitive emission lifetimes of hundreds of microseconds. The lifetime of the lowest energy singlet excited state, S1, was established by transient absorption spectroscopy and shows rapid deactivation (τ = 142 ps) by prompt fluorescence and intersystem crossing to the triplet state, T1. Time-dependent density functional theory (TD-DFT) calculations predict moderate ligand-to-metal charge transfer (LMCT) contributions of 25-30% for the S1 and T1 states. A comparison of Zr(bppda)2 to related zirconium pyridine dipyrrolide complexes, Zr(PDP)2, revealed important electronic structure changes due to the eight-coordinate ligand environment in Zr(bppda)2, which were correlated to differences in the photophysical properties between the two compound classes.

Delayed room temperature phosphorescence enabled by phosphines

Organic ultralong room-temperature phosphorescence (RTP) usually emerges instantly and immediately decays after excitation removal. Here we report a new delayed RTP that is postponed by dozens of milliseconds after excitation removal and decays in two steps including an initial increase in intensity followed by subsequent decrease in intensity. The delayed RTP is achieved through introduction of phosphines into carbazole emitters. In contrast to the rapid energy transfer from single-molecular triplet states (T1) to stabilized triplet states (Tn*) of instant RTP systems, phosphine groups insert their intermediate states (TM) between carbazole-originated T1 and Tn* of carbazole-phosphine hybrids. In addition to markedly increasing emission lifetimes by ten folds, since TM → Tn* transition require >30 milliseconds, RTP is thereby postponed by dozens of milliseconds. The emission character of carbazole-phosphine hybrids can be used to reveal information through combining instant and delayed RTP, realizing multi-level time resolution for advanced information, biological and optoelectronic applications.

Achieving Colorful Ultralong-Lifetime Room-Temperature Phosphorescence Based on Benzocarbazole Derivatives through Resonance Energy Transfer.

It is of practical significance to develop polymer-based room-temperature phosphorescence (RTP) materials with ultralong lifetime and multicolor afterglow. Herein, the benzocarbazole derivatives were selected and combined with a poly(vinyl alcohol) (PVA) matrix by a coassembly strategy. Owing to the hydrogen-bonding interactions between benzocarbazole derivatives and the PVA matrix, the nonradiative transition and the quenching of triplet excitons are effectively inhibited. Therefore, the maximum phosphorescence emission lifetime of 2202.17 ms from ABfCz-PVA and the maximum phosphorescence quantum efficiency of 34.97% from ABtCz-PVA were obtained, respectively. In addition, commercially available dye molecules were selected to construct phosphorescent resonance energy transfer (PRET) systems for energy acceptors, enabling full-color afterglow emission in blue, green, yellow, red, and even white. Based on the characteristics of prepared RTP materials, multifunctional applications to flexibility, information encryption, and erasable drawing were deeply explored.

Organometallic ruthenium complexes derived from anthracene and pyrene chromophores: Synthesis and photophysical properties

AbstractTwo new monopyridyl‐based Anthracene and Pyrene ligands were synthesized and employed to design Ruthenium‐coordinated organometallic complexes, RuAnthra and RuPyrene, respectively. The ligands and their metal complexes were fully characterized by different analytical techniques, including multinuclear 1D‐ and 2D‐NMR, electrospray ionization‐mass spectrometry, UV–Vis, fluorescence spectroscopy, and elemental analysis. Furthermore, their photophysical properties were studied in different solvents with increasing polarity using UV–Vis and fluorescence spectroscopy, showing less or no significant solvolysis effect. The average emission lifetimes of the complexes were further determined using time‐resolved emission spectroscopy. Additionally, the ligands and their metal complexes showed excellent ability to generate singlet oxygen and can be useful for several important potential applications.

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.

Improved midgap recombination lifetimes in GaN crystals grown by the low-pressure acidic ammonothermal method

To investigate the carrier recombination processes in GaN crystals grown by the low-pressure acidic ammonothermal (LPAAT) method, the photoluminescence (PL) spectra and PL lifetimes of LPAAT GaN crystals grown on acidic ammonothermal (AAT) GaN seed crystals were correlated with the growth polarity and species/concentration of point defects. The PL spectra of LPAAT GaN grown toward the (0001¯) direction (−c region), which provided the highest growth rate, exhibited a predominant near-band edge (NBE) emission. Neither bandgap narrowing nor Burstein–Moss shifts due to high concentration residual impurities were observed in the NBE emissions, indicating higher purity than the previously reported AAT GaN crystals. In addition, strain-induced energy shift or energy broadening of excitonic emission peaks was not observed, indicating excellent crystal coherency. Because of the reduced concentration of midgap recombination centers, a record-long room-temperature PL lifetime for the NBE emission of ammonothermal GaN (40 ps) was obtained from the −c region. Meanwhile, the PL spectra also exhibited the yellow and blue luminescence bands originating from particular deep-state radiative recombination centers. The major vacancy-type defects acting as midgap recombination centers are identified as vacancy complexes comprising a Ga vacancy (VGa) and a few N vacancies (VN), namely, VGa(VN)n buried by H and/or O, where n is an integer. Further reduction of such defect complexes will allow less compensated stable carrier concentration in the LPAAT GaN crystals.

Photoluminescence properties of Pr-doped LaAsO4: An experimental and theoretical study employing density functional theory

Praseodymium doped lanthanum arsenate, denoted as La1-xPrxAsO4, has been synthesized with different concentrations of the dopant (x = 0.5 %; 1 %; 2 %; 3 % and 5 %) via the combustion method and their optoelectronic properties have been investigated. A study of the crystalline structure and size of the compound by XRD confirms that both the pristine LaAsO4 and Pr-doped LaAsO4 are pure and maintain a monoclinic crystal structure, with the crystalline size ranging from 60 to 76 nm. The morphological study of the nanoparticles by SEM analysis reveals that all samples, regardless of the concentration of Pr3+, consist of homogeneously packed and irregularly shaped small particles. The optical studies by absorption and fluorescence spectroscopies highlight the unique optoelectronic characteristics of La1-xPrxAsO4, with absorption predominantly in the UV and blue regions and prominent emission peaks in the visible spectrum, most notably at 610 nm. The optimal luminescence is observed at a 0.5 % Pr3+ doping level, deviating from typical trends as higher concentrations lead to diminished emission intensity and lifetime due to concentration quenching effects. The application of Density Functional Theory (DFT) with GGA + PBE and GGA + PBE + U approximations has effectively elucidated the electronic structure and optical properties of the Pr-doped LaAsO4. The incorporation of Pr's 4f states within the LaAsO4 forbidden band significantly alters the material's electronic landscape, notably reducing the optical band gap from 4.45 eV to 2.299 eV. This modification in the band structure aligns favourably with the dielectric function curves and density of states analyses, corroborating the observed visible light emission in the doped samples.

Responsive organic room-temperature phosphorescence materials for spatial-time-resolved anti-counterfeiting

Stimulus-responsive room-temperature phosphorescence (RTP) materials have gained significant attention for their important optoelectronic application prospects. However, the fabrication strategy and underlying mechanism of stimulus-responsive RTP materials remain less explored. Herein, we present a reliable strategy for achieving pH-responsive RTP materials by integrating poly(vinyl alcohol) (PVA) with carboxylic acid or amino group functionalized terpyridine (Tpy) derivatives. The resulting Tpy derivatives-based RTP materials displayed reversible changes in emission color, intensity, and lifetime of both prompt and delayed emission. Notably, the RTP emission undergoes a significant diminish upon exposure to acid due to the protonation of Tpy units. Taking advantage of the decent RTP emission and pH-responsiveness of these RTP films, a spatial-time-resolved anti-counterfeiting application is demonstrated as a proof-of-concept for largely enhancing the security level. This study not only provides new prospects for developing smart RTP materials but also promotes the advancement of optical anti-counterfeiting applications.

High pH Stability and Ultralong‐Lived Room Temperature Phosphorescence Carbon Dots in Aqueous Environment

AbstractLong‐lived room temperature phosphorescence (RTP) materials have many potential applications in areas such as luminescent lighting, biological imaging, and information security owing to their unique optical properties. However, traditional RTP materials are challenged by the fact that their phosphorescence can be easily quenched by dissolved oxygen and solvent‐assisted relaxation, making it difficult for them to emit phosphorescence in aqueous solutions, particularly in extreme pH environments. In this study, a multicolor RTP carbon dot‐based composite material (u‐CDs) is developed with urea and 3‐aminophenylboronic acid as raw materials. This material exhibits ultra‐long phosphorescence emission lifetime and high pH stability by constructing a rigid hydrogen bond network structure in an aqueous environment. The u‐CDs have an optimal emission of 448 nm, a quantum yield of 21.6%, a phosphorescence lifetime of 2.35 s, and an afterglow time of more than 50 s. With such unique properties, u‐CDs have great potential for applications in anti‐counterfeiting, information encryption, and 3D printing.

Alkynyl Gold(I) Phosphine Complexes: Evaluation of Structure–Activity Relationships for the Alkynyl Ligands on Luminescence and Cytotoxicity

AbstractA series of gold (I) phoshpine complexes with diverse alkynyl ligands [Au(C≡CR)(PTA)] (R=C6H11OH, 1; C5H9OH, 2; C15H11OH, 3; C19H27O2, 4; C18H23O2, 5; C9H12N, 6; CH2OCH2C6H5, 7; C6H4OCH3, 8; PTA=1,3,5‐Triaza‐7‐phosphaadamantane) have been synthesized and characterized using a range of spectroscopic techniques. Complex 1 and 3 show an infinite one–dimensional S–type and zigzag aurophilic chain, respectively, whereas complex 2 containing 1‐ethynyl‐1‐cyclohexanol gives an approximate linear two–dimensional aurophilic chain, through intra/intermolecular Au(I)⋯Au(I) interactions as well as hydrogen bonding interactions between hydroxy groups of alkynyl ligands and PTA. Solid complexes 1–8 display strongly room/low–temperature emissive of 477–613 nm with the emission lifetime of 0.40–14.0 μs. All the complexes display higher cytotoxicities against MCF‐7, with the cytotoxicity decreasing in the following order 4&gt;8&gt;5&gt;3&gt;7&gt;6&gt;2&gt;1. Complex 4 and 5 stand out for the highest selectivity towards MCF–7 (IC50=0.63–0.78 μM) compared with normal human embryonic lung fibroblasts (helf) (IC50=14.85–18.13 μM), which makes those complexes attractive for breast cancer therapy.

Optimizing optical thermometry with tri-doped Ba2GdV3O11 phosphors: Ratiometric and fluorescence lifetime analysis

Optical sensor technology has undergone a transformative evolution with the advent of fluorescence ratio techniques (FIR) and fluorescence lifetime (FL) strategies, revolutionizing precision, performance, and reliability. This study delves into the synthesis of Ba2GdV3O11 phosphors doped with Ho3+/Nd3+, Er3+, and Yb3+, employing the sol-gel method for upconverting material fabrication. A thorough investigation into the structural, morphological, and optical properties of the synthesized phosphors is conducted. Excitation at 980 nm unveils upconversion (UC) emissions across green and red spectra. The intensities of the observed emission bands for Ho3+, Nd3+, and Er3+ demonstrate significant sensitivity to fluctuations in temperature. Temperature sensing relies on the 4S3/2 and 2H11/2 upconversion emissions bands, in addition to the emission lifetimes at 4S3/2. Enhanced thermal sensitivity values are attained, reaching up to 1.03 % K−1 and 1.07 % K−1 using the FIR strategy, and up to 0.146 % K−1 and 0.47 % K−1 with the FL strategy for Ho3+/Er3+/Yb3+ and Nd3+/Er3+/Yb3+ tri-doped Ba2GdV3O11 phosphors, respectively. Furthermore, the studied phosphors exhibit remarkable precision in detecting minute temperature changes (0.3 K), positioning them as promising candidates for precise temperature sensing. This study pioneers innovative methodologies to advance optical thermometry techniques, offering promising prospects for scientific and industrial applications reliant on precise optical temperature sensing.

Control of Quantized Spontaneous Emission from Single GaAs Quantum Dots Embedded in Huygens' Metasurfaces.

Advancements in photonic quantum information systems (QIS) have driven the development of high-brightness, on-demand, and indistinguishable semiconductor epitaxial quantum dots (QDs) as single photon sources. Strain-free, monodisperse, and spatially sparse local-droplet-etched (LDE) QDs have recently been demonstrated as a superior alternative to traditional Stranski-Krastanov QDs. However, integration of LDE QDs into nanophotonic architectures with the ability to scale to many interacting QDs is yet to be demonstrated. We present a potential solution by embedding isolated LDE GaAs QDs within an Al0.4Ga0.6As Huygens' metasurface with spectrally overlapping fundamental electric and magnetic dipolar resonances. We demonstrate for the first time a position- and size-independent, 1 order of magnitude increase in the collection efficiency and emission lifetime control for single-photon emission from LDE QDs embedded within the Huygens' metasurfaces. Our results represent a significant step toward leveraging the advantages of LDE QDs within nanophotonic architectures to meet the scalability demands of photonic QIS.

Thermally Prolonged NIR-II Luminescence Lifetimes by Cross-Relaxation.

Temperature regulates nonradiative processes in luminescent materials, fundamental to luminescence nanothermometry. However, elevated temperatures often suppress the radiative process, limiting the sensitivity of thermometers. Here, we introduce an approach to populating the excited state of lanthanides at elevated temperatures, resulting in a sizable lifetime lengthening and intensity increase of the near-infrared (NIR)-II emission. The key is to create a five-energy-level system and use a pair of lanthanides to leverage the cross-relaxation process. We observed the lifetime of NIR-II emission of Er3+ has been remarkably increased from 3.85 to 7.54 ms by codoping only 0.5 mol % Ce3+ at 20 °C and further increased to 7.80 ms when increasing the temperature to 40 °C. Moreover, this concept is universal across four ion pairs and remains stable within aqueous nanoparticles. Our findings emphasize the need to design energy transfer systems that overcome the constraint of thermal quenching, enabling efficient imaging and sensing.