Warm red light emitting Eu(III) complexes synthesis and analysis including computational methods for photonic applications.

Six luminescent europium organic complexes have been synthesized and studied for their luminescent properties. The synthesized complexes were analyzed through elemental analysis, XRD, SEM, EDAX, FT-IR, NMR and thermogravimetry. The complexes exhibit crystalline behavior and possess decent thermal stability. Photoluminescence study on complexes were conducted in both solid and solution states, the results indicate the characteristic red emission. With the addition of ancillary ligands, water molecules are replaced from inner coordination sphere, leading to enhanced luminescence properties. The colorimetric parameters (CIE, CP%, CCT, u', v') suggest aptness of these complexes in red light illuminating OLEDs. The J-O parameters were calculated experimentally and theoretically with the help of LUMPAC software. Theoretical and experimental results agree well reflecting the efficacy of the outcomes. As a result of red emission, these complexes could have interesting photonics applications. The biological studies indicate the probable use of these complexes in the medical industry.

PARAFAC under non-negativity constraint is adapted to recover the underlying Beer-Lambert law of the excitation-emission fluorescence matrix measurements acquired from analyte-triggered semiconductor QDs photoluminescence modulation. When and why?

BACKGROUND: Analyte-triggered semiconductor quantum dots (QDs) modulation in the presence of non-consistently responsive fluorescent species represents a challenging analytical issue in concrete multi-way data handling. QDs with heterogeneous sizes and/or uneven distribution of functional moieties on their surfaces exhibit significant fluctuations in the fluorescent response components, known as chemical rank, across different excitation/emission modes. This phenomenon may lead to a substantial deviation from the proportionality prescribed by Beer-Lambert law. Nonetheless, even in the presence of such deviation, a multi-way model may be successfully selected after determining a proper chemical rank in a QDs system. RESULTS: We show that in a valid PARAllel FACtor (PARAFAC) model under properly determined chemical rank, meaningfully resolved pure spectral profiles can be reached for each fluorescent responsive constituent in the original excitation-emission fluorescence matrix (EEFM) measurements. This was thoroughly illustrated by applying PARAFAC trilinear decomposition of a three-way data array of two distinct datasets acquired from semiconductor QDs sensing systems with low-rank trilinear assumption. The first dataset, presented here for the first time, comprises EEFM measurements of the ligand-driven quenching of thiomalic acid (TMA)-capped AgInS2 (AIS) QDs by vomitoxin. The second dataset, employed for illustrative purposes, comprises EEFM measurements of the quenching, via cation bridging, of glutathione (GSH)-capped CdTe QDs by Pb(II). The results of this study enabled the determination of vomitoxin at a ppb level in real samples of fish feeds, showcasing the efficacy of the PARAFAC model in resolving spectral signatures (loadings) and pure concentration profiles (scores). SIGNIFICANCE: PARAFAC under a properly examined chemical rank can be easily adapted for retrieval the underlying Beer-Lambert law of the original EEFM measurements with a low-rank trilinear structure through the chemically meaningful information either when (i) no deviation of Beer-Lambert law was observed as deeply discussed in connection with the dataset acquired from vomitoxin-driven molecular sensing through TMA-capped AIS QDs, or when (ii) substantial deviations of the Beer-Lambert law are evident, as discussed in connection with the dataset collected from sensing ionic species through Pb(II) bridging of GSH-capped CdTe QDs.

Extreme Electron-Photon Interaction in Disordered Perovskites.

The interaction of light with solids can be dramatically enhanced owing to electron-photon momentum matching. This mechanism manifests when light scattering from nanometer-sized clusters including a specific case of self-assembled nanostructures that form a long-range translational order but local disorder (crystal-liquid duality). In this paper, a new strategy based on both cases for the light-matter-interaction enhancement in a direct bandgap semiconductor - lead halide perovskite CsPbBr3 - by using electric pulse-driven structural disorder, is addressed. The disordered state allows the generation of confined photons, and the formation of an electronic continuum of static/dynamic defect states across the forbidden gap (Urbach bridge). Both mechanisms underlie photon-momentum-enabled electronic Raman scattering (ERS) and single-photon anti-Stokes photoluminescence (PL) under sub-band pump. PL/ERS blinking is discussed to be associated with thermal fluctuations of cross-linked [PbBr6]4- octahedra. Time-delayed synchronization of PL/ERS blinking causes enhanced spontaneous emission at room temperature. These findings indicate the role of photon momentum in enhanced light-matter interactions in disordered and nanostructured solids.

Indirect-To-Direct Bandgap Crossover and Room-Temperature Valley Polarization of Multilayer MoS2 Achieved by Electrochemical Intercalation.

Monolayer (1L) group VI transition metal dichalcogenides (TMDs) exhibit broken inversion symmetry and strong spin-orbit coupling, offering promising applications in optoelectronics and valleytronics. Despite their direct bandgap, high absorption coefficient, and spin-valley locking in K or K' valleys, the ultra-short valley lifetime limits their room-temperature applications. In contrast, multilayer TMDs, with more absorptive layers, sacrifice the direct bandgap and valley polarization upon gaining inversion symmetry from the bilayer structure. It is demonstrated that multilayer molybdenum disulfide (MoS2) can maintain 1) a structure with broken inversion symmetry and strong spin-orbit coupling, 2) a direct bandgap with high photoluminescence (PL) intensity, and 3) stable valley polarization up to room temperature. Through the intercalation of organic 1-ethyl-3-methylimidazolium (EMIM+) ions, multilayer MoS2 not only exhibits layer decoupling but also benefits from an electron doping effect. This results in a hundredfold increase in PL intensity and stable valley polarization, achieving 55% and 16% degrees of valley polarization at 3 K and room temperature, respectively. The persistent valley polarization at room temperature, due to interlayer decoupling and trion dominance facilitated by a gate-free method, opens up potential applications in valley-selective optoelectronics and valley transistors.

Synthesis and Optical Properties of Organic-Inorganic Hybrid [(18-Crown-6)K][MoOCl4(H2O)].

Crown ether anchored organic-inorganic hybrid halides have been recently reported as interesting luminescent materials in the visible region of electromagnetic spectrum. Is it possible to develop such crown ether anchored hybrid materials for near infrared emission? Motivated by this question, we designed a new hybrid material, namely, [(18-Crown-6)K][MoOCl4(H2O)]. 18-Crown-6 ether bound with K+ form the cationic part [(18-Crown-6)K]+. The K+ of [(18-Crown-6)K]+ electrostatically interacts with Cl- of the anionic part [MoOCl4(H2O)]-, forming the hybrid crystal [(18-Crown-6)K][MoOCl4(H2O)]. It crystallizes in orthorhombic crystal system with Pnma space group. The Mo(V) possesses one d-electron (d1) in C4v point group symmetry in the [MoOCl4(H2O)]- polyhedra. This electronic configuration leads to multiple spin-allowed d-d transitions along with a ligand to metal charge transfer (LMCT) resulting into multiple optical absorption bands in the near UV-visible-near infrared (NIR) region. The lowest energy d-d transition via 2E  to 2B2 leads to NIR PL with peak at 952 nm, but with a poor intensity at room temperature.

Photoluminescent and Electrochemiluminescent Detection of Fe3+ Using Cyclometalated Iridium Complexes via Fe3+-Catalyzed Hydrolysis.

Ferric ion (Fe3+) is a biologically abundant and important metal ion. We developed several cyclometalated iridium complex-based molecular sensors (1, ppy-1, 1-phen, 1a, and 1-OMe) for the detection of Fe3+ using an acetal moiety as the reaction site. The acetal moiety in iridium complexes undergoes Fe3+-catalyzed hydrolysis and subsequent formation of a formyl group, resulting in turn-off photoluminescent and electrochemiluminescent responses. Sensor 1 showed excellent selectivity toward Fe3+ over other biologically important metal ions. Furthermore, we compared the performance of the sensors based on the structural differences of the iridium complexes, and revealed a relationship between the structure and chemical properties through electrochemical experiments and computational calculations.

Green Protocol for the Synthesis of Luminescent Carbon Nanodots Derived from Murraya Koenigii Leaves and Urea: Enhancing Photoluminescence for Advanced Bioimaging.

We have synthesized Murraya Koenigii leaves powder-derived carbon nanodots (CNDs) by hydrothermal method. A tribute to our commitment to environmental sustainability is the unique composition of our CNDs, which are made entirely of natural carbon sources and a green solvent, water. Our further efforts to improve performance led us to start making nitrogen-doped CNDs. By using urea as a non-toxic source of nitrogen, we observed a substantial increase in fluorescence intensity, extending the usefulness and potential of these nanomaterials. We investigated the optical properties using UV-Vis and fluorescence spectroscopy. The other parameters, like structural and size-shape morphology, were analyzed using FTIR, XRD, and HR-TEM, respectively. The fluorescence spectroscopy demonstrated their capability to exhibit wavelength-dependent photoluminescence (PL), highlighting the potential of these CNDs for cell bioimaging applications. The fluorescence properties affirm their suitability for biomedical applications, as they do not involve any inherent risk to cells.

Shortwave-Infrared Silver Chalcogenide Quantum Dots for Optoelectronic Devices.

Silver chalcogenide (Ag2X, X = S, Se, Te) semiconductor quantum dots (QDs) have been extensively studied owing to their short-wave infrared (SWIR, 900-2500 nm) excitation and emission along with lower solubility product constant and environmentally benign nature. However, their unsatisfactory photoluminescence quantum yields (PLQYs) make it difficult to obtain optoelectronic devices with high performances. To tackle this challenge, researchers have made great efforts to develop valid strategies to improve the PLQYs of SWIR Ag2X QDs by suppressing their nonradiative recombination of excitons. In this Perspective, we summarize the significant approaches of heteroatom doping and surface passivation to enhance the PLQYs of SWIR Ag2X QDs, and we conclude their application in high-efficiency optoelectronic devices. Finally, we examine the future trends and promising opportunities of Ag2X QDs with regard to their optical properties and optoelectronics. We believe that this Perspective will serve as a valuable reference for future advancement in the synthesis and application of SWIR Ag2X QDs.

Needle Tip Tracking through Photoluminescence for Minimally Invasive Surgery.

Minimally invasive surgery continues to prioritize patient safety by improving imaging techniques and tumor detection methods. In this work, an all-optical alternative to the current image based techniques for in vitro minimally invasive procedures has been explored. The technique uses a highly fluorescent marker for the surgical needle to be tracked inside simulated tissues. A series of markers were explored including inorganic (Perovskite and PbS) and organic (carbon dots) nanoparticles and organic dye (Rhodamine 6G) to identify layers of different stiffnesses within a tissue. Rhodamine 6G was chosen based on its high fluorescence signal to track 3D position of a surgical needle in a tissue. The needle was tracked inside homogeneous and inhomogeneous gelatin tissues successfully. This exploratory study of tissue characterization and needle tip tracking using fluorescent markers or photoluminescence technique show potential for real-time application of robot-assisted needle insertions during in vivo procedures.

Comparison of Survivin Determination by Surface-Enhanced Fluorescence and Raman Spectroscopy on Nanostructured Silver Substrates.

Survivin belongs to a family of proteins that promote cellular proliferation and inhibit cellular apoptosis. Its overexpression in various cancer types has led to its recognition as an important marker for cancer diagnosis and treatment. In this work, we compare two approaches for the immunochemical detection of survivin through surface-enhanced fluorescence or Raman spectroscopy using surfaces with nanowires decorated with silver nanoparticles in the form of dendrites or aggregates as immunoassays substrates. In both substrates, a two-step non-competitive immunoassay was developed using a pair of specific monoclonal antibodies, one for detection and the other for capture. The detection antibody was biotinylated and combined with streptavidin labeled with rhodamine for the detection of surface-enhanced fluorescence, while, for the detection via Raman spectroscopy, streptavidin labeled with peroxidase was used and the signal was obtained after the application of 3,3',5,5'-tetramethylbenzidine (TMB) precipitating substrate. It was found that the substrate with the silver dendrites provided higher fluorescence signal intensity compared to the substrate with the silver aggregates, while the opposite was observed for the Raman signal. Thus, the best substrate was used for each detection method. A detection limit of 12.5 pg/mL was achieved with both detection approaches along with a linear dynamic range up to 500 pg/mL, enabling survivin determination in human serum samples from both healthy and ovarian cancer patients for cancer diagnosis and monitoring purposes.

Aqueous phase transfer of near-infrared ZnCuInS2/ZnS quantum dots: Synthesis and characterization.

Cadmium-free and NIR fluorescent QDs are promising candidates for bio-application. Thus, we present the synthesis of ternary ZnCuInS2/ZnS (ZCIS/ZnS) quantum dots (QDs) where the molar variation of Cu/Zn of the precursors was used to tune the optical and structural properties. QDs with Cu/Zn molar ratio of 2/1 passivated with ZnS exhibited the best optical properties. They showed dominant near-infrared photoluminescence (approx. 850 nm) and highest quantum yield (approx. 52 %, λexc = 500 nm). Therefore, they were further subject to modification to ensure their transfer to the aqueous phase and improve biocompatibility. For this, different functionalization approaches were used. The first method relied on encapsulation with polymers like PSMA (poly(styrene co-maleic anhydride)) and PMAO (poly(maleic anhydride-alt-1-octadecene) coupled with polyetheramine (JEFF; Jeffamine M-1000), and the second relied on hydrophilization with PMAO. Furthermore, we also applied a surface ligand exchange process using DHLA (dihydrolipoic acid) and polyethylene glycol (PEG)-appended DHLA. The comprehensive study indicated that ZnCuInS2/ZnS QDs functionalized with PMAO (ZnCuInS2/ZnS@PMO) exhibited the highest photoluminescence (PL QY) along with ensured high colloidal stability in aqueous media. Moreover, no noticeable deterioration of the photoluminescence profile was observed for all used functionalization approaches. However, a significant decrease in QY was observed for almost all functionalized QDs except those that were PMO-capped. The synthesized QDs were systematically characterized by transmission electron microscopy (TEM), powder X-ray diffraction (XRD), UV-Vis absorption spectroscopy, and fluorescence spectroscopy. Biological studies indicate that the obtained hydrophilic ZCIS QDs are biocompatible and localized intracellularly inside endosomes.

Modeling Temperature-Dependent Photoluminescence Dynamics of Colloidal CdS Quantum Dots Using Long Short-Term Memory (LSTM) Networks.

This study addresses the challenge of modeling temperature-dependent photoluminescence (PL) in CdS colloidal quantum dots (QD), where PL properties fluctuate with temperature, complicating traditional modeling approaches. The objective is to develop a predictive model capable of accurately capturing these variations using Long Short-Term Memory (LSTM) networks, which are well suited for managing temporal dependencies in time-series data. The methodology involved training the LSTM model on experimental time-series data of PL intensity and temperature. Through numerical simulation, the model's performance was assessed. Results demonstrated that the LSTM-based model effectively predicted PL trends under different temperature conditions. This approach could be applied in optoelectronics and quantum dot-based sensors for enhanced forecasting capabilities.

An investigation on the structural, morphological, optical, and antibacterial activity of Sr:CuS nanostructures.

The aim of the present study is to synthesize Cu1-xSrxS (x = 0.00, 0.025, 0.05, 0.075, and 0.1) nanoparticles (NPs) using an easy chemical co-precipitation method in an efficient, inexpensive, and simple technique. The structural, morphological, and optical properties of the prepared samples were investigated using XRD, TEM, XRF, UV-Vis DRS, and PL characterization techniques. XRD spectra confirmed the Sr-doped copper sulfide nanoparticles have a hexagonal structure with crystallite sizes ranging from 15.15 to 16.04 nm, and, by XRF, the presence of the dopant was detected. TEM analysis confirmed that strontium ions had an effect on the shape of the CuS nanostructure, and the particle size increased from 16.27 to 17.32 nm after doping. A study using UV-Vis showed the presence of Sr doping increased the optical energy band gap (1.38 eV to 1.59 eV). At room temperature, one photoluminescence (PL) band was found at 826 nm. The antibacterial activity of CuS nanostructures against E. coli, P. aeruginosa, Klebsiella pneumonia, and S. aureus was evaluated by zone of inhibition. Sr doped CuS NPs exhibited the highest antibacterial activity against S. aureus (17 to 29 mm). Also, the results demonstrated that samples doped with 5, 7.5, and 10% Sr exhibited inhibitory effects against all the tested microbial strains higher than the antibiotic.

Giant Valley Zeeman Splitting in Vanadium-Doped WSe2 Monolayers.

2D dilute magnetic semiconductors (DMS) based on transition metal dichalcogenides (TMD) offer an innovative pathway for advancing spintronic technologies, including the potential to exploit phenomena such as the valley Zeeman effect. However, the impact of magnetic ordering on the valley degeneracy breaking and on the enhancement of the optical transitions g-factors of these materials remains an open question. Here, a giant effective g-factors ranging between ≈-27 and -69 for the bound exciton at 4 K in vanadium-doped WSe2 monolayers, obtained through magneto-photoluminescence (PL) experiments is reported. This giant g-factor disappears at room temperature, suggesting that this response is associated with a magnetic ordering of the vanadium impurity states at low temperatures. Ab initio calculations for the vanadium-doped WSe2 monolayer confirm the existence of magnetic ordering of the vanadium states, which leads to degeneracy breaking of the valence bands at K and K'. A phenomenological analysis is employed to correlate this splitting with the measured enhanced effective g-factor. The findings shed light on the potential of defect engineering of 2D materials for spintronic applications.

Suppressing energy migration via antiparallel spin alignment in one-dimensional Mn2+ halide magnets with high luminescence efficiency.

Photoexcited energy migration is prone to causing luminescence quenching in Mn2+ luminescent materials, presenting a formidable challenge for optoelectronic applications. Although various strategies and mechanisms have been proposed to mitigate this issue, the role of spin alignment between adjacent Mn2+ ions has remained largely unexamined. In this study, we have elucidated the influence of spin alignment on energy migration within the one-dimensional Mn2+-metal halide compound (CH3)4NMnCl3 (TMMC) through variable-temperature photoluminescence (PL) and magnetic-optical spectroscopy. This investigation was conducted with reference to (CH6N3)2MnCl4 (GUA) with isolated [Mn3Cl12]6- trimers and Cd2+-doped TMMC. The spin order in TMMC below approximately 55 K is demonstrated by the disorder-order transition observed in the temperature-dependent magnetic susceptibility. This finding is further corroborated by the negligible shift in the temperature- and field-dependent emission peaks, a consequence of magnetic saturation. Our results indicate that the antiparallel spin alignment along the Mn2+ chain in TMMC effectively suppresses energy migration and multiphonon relaxation, thereby reducing nonradiative transitions and enhancing the photoluminescence quantum yield (PLQY).This research casts new light on the potential for developing high-performance Mn2+-doped phosphors for optoelectronic and spin-photonic applications, offering insights into the manipulation of spin and energy dynamics in these materials.

Flexible X-ray Imaging and Stable Information Storage of SrF2:Eu Based on Radio-Photoluminescence.

X-ray imaging has garnered widespread interest in biomedical diagnosis and nondestructive detection. The exploration of radio-photoluminescence has hastened the advancement of X-ray information storage. However, significant challenges persist in achieving the prolonged imaging of curved objects without attenuation. Here, europium-doped strontium fluoride (SrF2:Eu) is meticulously created to exhibit a linear response to an extensive range of X-ray doses (maximum dose > 5000 Gy), showcasing excellent X-ray information reading/erasing reusability properties (10 cycles). This is accompanied by a red-to-blue emission transition under UV excitation, sustaining for 150 days without attenuation. To elucidate the phenomena of irradiated photoluminescent discoloration and the reversible X-ray storage of SrF2:Eu, we propose an electron-vacancy trap (valence conversion) mechanism, information stably retained by the SrF2:Eu-based device under ambient conditions due to high energy barriers. The time-lapse readout capability is further demonstrated for three-dimensional imaging of curved objects (10 lp mm-1) based on SrF2:Eu embedded within a polydimethylsiloxane (SrF2:Eu@PDMS). The SrF2:Eu demonstrates time-lapse imaging, reversible radio-photoluminescence, and recoverable X-ray storage, offering a promising avenue for optical information encryption and anticounterfeiting applications.

Bayesian Optimization for Controlled Chemical Vapor Deposition Growth of WS2.

We applied Bayesian optimization (BO), a machine learning (ML) technique, to optimize the growth conditions of monolayer WS2 using photoluminescence (PL) intensity as the objective function. Through iterative experiments guided by BO, an improvement of 86.6% in PL intensity is achieved within 13 optimization rounds. Statistical analysis revealed the relationships between growth conditions and PL intensity, highlighting the importance of critical conditions, including the tungsten source concentration and Ar flow rate. Furthermore, the effectiveness of BO is demonstrated by comparison with random search, showing its ability to converge to optimal conditions with fewer iterations. This research highlights the potential of ML-driven approaches in accelerating material synthesis and optimization processes, paving the way for advances in two-dimensional (2D) material-based technologies.

Large-scale heterogeneous synthesis of monodisperse high performance colloidal CsPbBr3 nanocrystals.

Colloidal lead halide perovskite nanocrystals (LHP NCs) are promising semiconductor materials for optoelectronic devices, but the high ionicity of LHP NCs makes their crystallization control and post-treatment difficult. Here, phosphonic acids (PAs) are employed as ligands to design a solid-liquid heterogeneous reaction system to regulate the LHP NC crystallization and achieve the desired focusing growth. During the heterogeneous synthesis, the precursors in the liquid phase are responsible for the burst nucleation and initial growth of NCs. Afterwards, the focusing growth of NCs is supported by the precursors released from the solid phase. In addition, the strong binding ability of PAs enables effective passivation of LHP NCs. Without post-treatment, gram-scale monodisperse CsPbBr3 NCs having photoluminescence with a full width at half-maximum of 18 nm and a quantum yield of near-unity are obtained. The CsPbBr3 NCs covered by a compact ligand layer keep initial quantum yield even after 18 cycles of purification, exhibiting excellent stability against polar solvents, ultraviolet irradiation and heat treatment. As scintillators, the prepared CsPbBr3 NCs show strong radioluminescence emission and high-resolution X-ray imaging.

Multimodal Temperature Readout Boosts the Performance of CuInS2/ZnS Quantum Dot Nanothermometers.

Fluorescent nanothermometers are positioned to revolutionize research into cell functions and provide strategies for early diagnostics. Fluorescent nanostructures hold particular promise to fulfill this potential if nontoxic, stable varieties allowing for precise temperature measurement with high thermal sensitivities can be fabricated. In this work, we investigate the performance of micelle-encapsulated CuInS2/ZnS core/shell colloidal quantum dots (QDs) as fluorescent nanothermometers. We demonstrate four temperature readout modes, which are based on variations in the photoluminescence intensity, energy, and lifetime and on a specific ratio of excitation efficiencies. We further leverage this multimodal readout to construct a fifth, multiparametric thermometer calibration based on the multiple linear regression (MLR) model. We show that the MLR approach boosts the thermometer sensitivity by up to 7-fold while reducing the readout error by about a factor of 3. As a result, our QDs offer the highest sensitivities among semiconducting QDs emitting in the first biological window. The obtained results indicate that CuInS2/ZnS QDs are excellent candidates for intracellular in vivo thermometry and provide guidelines for further optimization of their performance.

Strong Grain Boundary Passivation Effect of Coevaporated Dopants Enhances the Photoemission of Lead Halide Perovskites.

Herein, we demonstrate that coevaporated dopants provide a means to passivate buried interfacial defects occurring at perovskite grain boundaries in evaporated perovskite thin films, thus giving rise to an enhanced photoluminescence. By means of an extensive photophysical characterization, we provide experimental evidence that indicate that the codopant acts mainly at the grain boundaries. They passivate interfacial traps and prevent the formation of photoinduced deep traps. On the other hand, the presence of an excessive amount of organic dopant can lead to a barrier for carrier diffusion. Hence, the passivation process demands a proper balance between the two effects. Our analysis on the role of the dopant, performed under different excitation regimes, permits evaluation of the performance of the material under conditions more adapted to photovoltaic or light emitting applications. In this context, the approach taken herein provides a screening method to evaluate the suitability of a passivating strategy prior to its incorporation into a device.