Nonradiative Decay Channels Research Articles

Highly Efficient Near-Infrared Luminescent Radicals with Emission Peaks over 750 nm.

Purely organic molecules exhibiting near-infrared (NIR) emission possess considerable potential for applications in both biological and optoelectronic technological domains, owing to their inherent advantages such as cost-effectiveness, biocompatibility, and facile chemical modifiability. However, the repertoire of such molecules with emission peaks exceeding 750 nm and concurrently demonstrating high photoluminescence quantum efficiency (PLQE) remains relatively scarce due to the energy gap law. Herein, we report two open-shell NIR radical emitters, denoted as DMNA-Cz-BTM and DMNA-PyID-BTM, achieved through the strategic integration of a donor group (DMNA) onto the Cz-BTM and PyID-BTM frameworks, respectively. We found that the donor-acceptor molecular structure allows the two designed radical emitters to exhibit a charge-transfer excited state and spatially separated electron and hole levels with non-bonding characteristics. Thus, the high-frequency vibrations are effectively suppressed. Besides, the reduction of low-frequency vibrations is observed. Collectively, the non-radiative decay channel is significantly suppressed, leading to exceptional NIR PLQE values. Specifically, DMNA-Cz-BTM manifests an emission peak at 758 nm alongside a PLQE of 55 %, whereas DMNA-PyID-BTM exhibits an emission peak at 778 nm with a PLQE of 66 %. Notably, these represent the pinnacle of PLQE among metal-free organic NIR emitters with emission peaks surpassing 750 nm.

Moiré-engineered light-matter interactions in MoS2/WSe2 heterobilayers at room temperature

Moiré superlattices in van der Waals heterostructures represent a highly tunable quantum system, attracting substantial interest in both many-body physics and device applications. However, the influence of the moiré potential on light-matter interactions at room temperature has remained largely unexplored. In our study, we demonstrate that the moiré potential in MoS2/WSe2 heterobilayers facilitates the localization of interlayer exciton (IX) at room temperature. By performing reflection contrast spectroscopy, we demonstrate the importance of atomic reconstruction in modifying intralayer excitons, supported by the atomic force microscopy experiment. When decreasing the twist angle, we observe that the IX lifetime becomes longer and light emission gets enhanced, indicating that non-radiative decay channels such as defects are suppressed by the moiré potential. Moreover, through the integration of moiré superlattices with silicon single-mode cavities, we find that the devices employing moiré-trapped IXs exhibit a significantly lower threshold, one order of magnitude smaller compared to the device utilizing delocalized IXs. These findings not only encourage the exploration of many-body physics in moiré superlattices at elevated temperatures but also pave the way for leveraging these artificial quantum materials in photonic and optoelectronic applications.

Phonon-assisted Auger decay of excitons in doped transition metal dichalcogenide monolayers.

The competition between the radiative and nonradiative lifetimes determines the optical quantum yield and plays a crucial role in the potential optoelectronic applications of transition metal dichalcogenides (TMDCs). Here, we show that, in the presence of free carriers, an additional nonradiative decay channel opens for excitons in TMDC monolayers. Although the usual Auger decay channel is suppressed at low doping levels by the simultaneous momentum and energy conservation laws, exciton-phonon coupling relaxes this suppression. By solving a Bethe-Salpeter equation, we calculate the phonon-assisted Auger decay rates in four typical TMDCs as a function of doping, temperature, and dielectric environment. We find that even for a relatively low doping of 1012 cm-2, the nonradiative lifetime ranges from 16 to 165ps in different TMDCs, offering competition to the radiative decay channel.

Investigation of the Nonradiative Photoprocesses of Unnatural DNA Base: 7-(2-Thienyl)-imidazo[4,5-b]pyridine (Ds)─A Computational Study.

7-(2-Thienyl)-imidazo[4,5-b]pyridine (Ds) is an unnatural nucleic acid that forms a stable pair with pyrrole-2-carbaldehyde (Pa) in DNA. This Ds-Pa pair gets stabilized via van der Waals interaction and shape fitting. In our previous study [Ghosh, P. J. Phys. Chem. A 2021, 125, 5556-5561], we investigated the nonradiative photoprocesses of the unnatural DNA base Pa, and also there are some studies on its stability and reactivity in the ground state. But, to consider it as a good unnatural base pair, one has to understand its stability not only in the ground state but also in the excited states after absorbing ultraviolet (UV) radiation. Therefore, in this study, the excited-state photoprocesses of Ds on UV irradiation and its nonradiative decay channels have been investigated using state-of-the-art multireference methods, and this investigation finally leads the molecule to access the minimum energy crossing point (MECP) via a downhill pathway.

Topologically Protected Photovoltaics in Bi Nanoribbons.

Photovoltaic efficiency in solar cells is hindered by many unwanted effects. Radiative channels (emission of photons) sometimes mediated by nonradiative ones (emission of phonons) are principally responsible for the decrease in exciton population before charge separation can take place. One such mechanism is electron-hole recombination at surfaces or defects where the in-gap edge states serve as the nonradiative channels. In topological insulators (TIs), which are rarely explored from an optoelectronics standpoint, we show that their characteristic surface states constitute a nonradiative decay channel that can be exploited to generate a protected photovoltaic current. Focusing on two-dimensional TIs, and specifically for illustration purposes on a Bi(111) monolayer, we obtain the transition rates from the bulk excitons to the edge states. By breaking the appropriate symmetries of the system, one can induce an edge charge accumulation and edge currents under illumination, demonstrating the potential of TI nanoribbons for photovoltaics.

Surfactant-based supramolecular dye assembly: A highly selective and economically viable platform for quantification of heparin antidote

Herein, we have employed a supramolecular assembly of a cationic dye, LDS-698 and a common surfactant sodium dodecyl sulfate (SDS) as a turn-on fluorescent sensor for protamine (Pr) detection. Addition of cationic Pr to the solution of dye-surfactant complex brings negatively charged SDS molecules together through strong electrostatic interaction, assisting aggregation of SDS way before its critical micellar concentration (CMC). These aggregates encapsulate the dye molecules within their hydrophobic region, arresting non-radiative decay channels of the excited dye. Thus, the LDS-698•SDS assembly displays substantial enhancement in fluorescence intensity that follows a nice linear trend with Pr concentration, providing limit of detection (LOD) for Pr as low as 3.84(±0.11) nM in buffer, 124.4(±6.7) nM in 1% human serum and 28.3(±0.5) nM in 100% human urine. Furthermore, high selectivity, low background signal, large stokes shift, and emission in the biologically favorable deep-red region make the studied assembly a promising platform for Pr sensing. As of our knowledge it is the first ever Pr sensory platform, using a very common surfactant (SDS), which is economically affordable and very easily available in the market. This innovative approach can replace the expensive, exotic and specialized chemicals considered for the purpose and thus showcase its potential in practical applications.

Unraveling non-radiative decay channels of exciplexes to construct efficient red emitters for organic light-emitting diodes.

Exciplex emitters naturally have thermally activated delayed fluorescence characteristics due to their spatially separated molecular orbitals. However, the intermolecular charge transfer potentially induces diverse non-radiative decay channels, severely hindering the construction of efficient red exciplexes. Thus, a thorough comprehension of this energy loss is of paramount importance. Herein, different factors, including molecular rigidity, donor-acceptor interactions and donor-donor/acceptor-acceptor interactions, that impact the non-radiative decay were systematically investigated using contrasting exciplex emitters. The exciplex with rigid components and intermolecular hydrogen bonds showed a photoluminescence quantum yield of 84.1% and a singlet non-radiative decay rate of 1.98 × 106 s-1 at an optimized mixing ratio, respectively, achieving a 3.3-fold increase and a 70% decrease compared to the comparison group. In the electroluminescent device, a maximum external quantum efficiency of 23.8% was achieved with an emission peak of 608 nm, which represents the state-of-the-art organic light-emitting diodes using exciplex emitters. Accordingly, a new strategy is finally proposed, exploiting system rigidification to construct efficient red exciplex emitters that suppress non-radiative decay.

Confined semiconducting polymers with boosted NIR light-triggered H2O2 production for hypoxia-tolerant persistent photodynamic therapy.

Hypoxia featured in malignant tumors and the short lifespan of photo-induced reactive oxygen species (ROS) are two major issues that limit the efficiency of photodynamic therapy (PDT) in oncotherapy. Developing efficient type-I photosensitizers with long-term ˙OH generation ability provides a possible solution. Herein, a semiconducting polymer-based photosensitizer PCPDTBT was found to generate 1O2, ˙OH, and H2O2 through type-I/II PDT paths. After encapsulation within a mesoporous silica matrix, the NIR-II fluorescence and ROS generation are enhanced by 3-4 times compared with the traditional phase transfer method, which can be attributed to the excited-state lifetime being prolonged by one order of magnitude, resulting from restricted nonradiative decay channels, as confirmed by femtosecond spectroscopy. Notably, H2O2 production reaches 15.8 μM min-1 under a 730 nm laser (80 mW cm-2). Further adsorption of Fe2+ ions on mesoporous silica not only improves the loading capacity of the chemotherapy drug doxorubicin but also triggers a Fenton reaction with photo-generated H2O2 in situ to produce ˙OH continuously after the termination of laser irradiation. Thus, semiconducting polymer-based nanocomposites enables NIR-II fluorescence imaging guided persistent PDT under hypoxic conditions. This work provides a promising paradigm to fabricate persistent photodynamic therapy platforms for hypoxia-tolerant phototheranostics.

Synergetic Enhancement of Quantum Yield and Exciton Lifetime of Monolayer WS2 by Proximal Metal Plate and Negative Electric Bias.

The efficiency of light emission is a critical performance factor for monolayer transition metal dichalcogenides (1L-TMDs) for photonic applications. While various methods have been studied to compensate for lattice defects to improve the quantum yield (QY) of 1L-TMDs, exciton-exciton annihilation (EEA) is still a major nonradiative decay channel for excitons at high exciton densities. Here, we demonstrate that the combined use of a proximal Au plate and a negative electric gate bias (NEGB) for 1L-WS2 provides a dramatic enhancement of the exciton lifetime at high exciton densities with the corresponding QY enhanced by 30 times and the EEA rate constant decreased by 80 times. The suppression of EEA by NEGB is attributed to the reduction of the defect-assisted EEA process, which we also explain with our theoretical model. Our results provide a synergetic solution to cope with EEA to realize high-intensity 2D light emitters using TMDs.

Fluorescence based studies on the interaction and characterization of surface-active ionic liquids with polarity sensitive intramolecular charge transfer probe

Surface-active ionic liquids (SAILs) are of tremendous interest in recent times due to their improved application in the field of food, detergent, and health. The modulated fluorescence behavior of an intramolecular charge transfer (ICT) probe, trans‐ethyl‐p‐(dimethylamino) cinnamate (EDAC), in presence of five different SAILs with varying head groups (viz. imidazolium, pyridinium, and morpholinium) and different alkyl chain length (decyl, dodecyl, and tetradecyl) was monitored by steady state and time-resolved fluorescence spectroscopy. Extreme sensitivity of EDAC fluorescence was used to characterize different physicochemical properties of the SAILs, including critical micelle concentration, static polarity, and empirical solvent polarity scale, ET(30) of the microenvironment. The estimated parameters are in good agreement with the literature reports and measured independently from other complimentary experiments discussed here. Time‐resolved fluorescence experiments show a significant retardation in different nonradiative decay channels of EDAC, when compared to that in aqueous phase, indicating a preferential association of the probe in presence of SAILs. The results indicate that the physicochemical properties of SAILs can be tuned by controlling the nature of both the cations and as well as the chain length of the alkyl group. These properties also show significant modulation in solutions with varying SAIL concentration, particularly in the pre- and post-micellar region. The results, particularly the surface-active properties and the self-assembly behavior presented in this study, are expected to provide new knowledge towards the design and development of novel SAILs with specific industrial and biological applications.

Enhancing Up-Conversion Luminescence Using Dielectric Metasurfaces: Role of the Quality Factor of Resonance at a Pumping Wavelength.

Photonic applications of up-conversion luminescence (UCL) suffer from poor external quantum yield owing to a low absorption cross-section of UCL nanoparticles (UCNPs) doped with lanthanide ions. In this regard, plasmonic nanostructures have been proposed for enhancing UCL intensity through strong electromagnetic local-field enhancement; however, their intrinsic ohmic loss opens additional nonradiative decay channels. Herein, we demonstrate that dielectric metasurfaces can overcome this disadvantage. A periodic array of amorphous-silicon nanodisks serves as a metasurface on which a layer of UCNPs is self-assembled. Sharp resonances supported by the metasurface overlap the absorption wavelength (λ = 980 nm) of UCNPs to excite them, resulting in the enhancement of UCL intensity. We further sharpen the resonances through rapid thermal annealing (RTA) of the metasurface, crystallizing silicon to reduce intrinsic optical losses. By optimizing the RTA condition (at 1000 °C for 20 min in N2/H2 (3 vol %) atmosphere), the resonance quality factor improves from 17.2 to 32.9, accompanied by an increase in the enhancement factor of the UCL intensity from 86- to over 600-fold. Moreover, a reduction in the intrinsic optical losses mitigates the UCL thermal quenching under a high excitation density. These findings provide a strategy for increasing light-matter interactions in nanophotonic composite systems and promote UCNP applications.

Berberine and cyclodextrin based supramolecular assembly for the detection of a cancer biomarker in complex biomatrices via indicator displacement assay

Spermine, an aliphatic tetramine plays a vital role in the growth and proliferation of cells. When tissues undergo growth-promoting hormonal stimulation, the concentration of spermine increases within the body. However, an elevated level of spermine in biological matrices like urine and serum is considered to be an effective indicator of various physiological disorders, specially the presence of malignant tissues within the body. Therefore, it is highly rewarding to accurately determine the concentration of spermine by an instant, label free, user friendly method. Herein, we present a supramolecular assembly of berberine (BBR) and sulfobutylether beta cyclodextrin (SBE10βCD) as fluorescent probe for the quantification of spermine in complex bio-media. Formation of the BBR-SBE10βCD supramolecular assembly upon incorporation of BBR into the SBE10βCD cavity results in a significant increase in fluorescence intensity of the dye due to the reduction in its non-radiative decay channels. While spermine is introduced into the complex solution, it strongly binds with the polyanionic host, displacing BBR from the host cavity. This causes a dramatic reduction of the fluorescence intensity, which follows a linear trend as a function of spermine concentration. Thus, from the linear regression analysis of such fluorescence response, limit of detection (LOD) of spermine has been determined to be 0.8 µM and 1.49 µM, in 1% serum and 50% urine matrices respectively. This outcome showcases the practicality and suitability of the investigated system in the field of bio-sensing. Furthermore, excellent biocompatibility of both BBR and SBE10βCD, emission in the green region of the electromagnetic spectrum, well separated absorption and emission profiles make the studied supramolecular assembly a preferred choice for the initial diagnosis of malignant tissues within the body via indicator displacement assay (IDA).

Stimulated-emission cross-sections of trivalent erbium ions in the cubic sesquioxides Y2O3, Lu2O3, and Sc2O3

We report on a detailed revision of the spectroscopic properties of Er3+ ions in the cubic sesquioxide host crystals R2O3 (R = Y, Lu and Sc). The 4f-4f transition probabilities are calculated by applying a modified Judd-Ofelt theory accounting for configuration interaction based on the measured absorption spectra. The stimulated-emission cross-sections for the 4I11/2 → 4I13/2 (at ∼2.8 µm) and 4I13/2 → 4I15/2 (at ∼1.6 µm) transitions of Er3+ ions are determined and the luminescence dynamics from the 4I11/2 and 4I13/2 manifolds are studied at different temperatures. It is found that the luminescence lifetime of the 4I11/2 state strongly depends on the host-forming R3+ cation even at low temperatures due to a non-negligible non-radiative multiphonon decay channel. Er:Y2O3 exhibits the lowest phonon energies and consequently the longest 4I11/2 luminescence lifetimes. A disagreement between the absorption and emission probabilities for the 4I15/2 ↔ 4I11/2 transition of Er3+ ions is observed at room temperature and explained considering the distribution of Er3+ ions over two non-equivalent crystallographic sites, C2 and C3i.

Investigation of annealing effects on structural, morphological, optical, chemical, and luminescent properties of (K,Na)NbO3 thin films

Here, (K,Na)NbO3 (KNN) films were synthesized using RF sputtering under Ar:O2 (3:1) environment, and eventually annealed by rapid thermal annealing (RTA), and conventional furnace annealing (CFA), at different temperatures. Crystalline films are observed with the evolution of well-shaped regular features of KNN perovskite after annealing, but the growth scenario is different in RTA and CFA. XPS results reveal the formation of an additional hump of Nb sub-oxides upon annealing via both processes. The transmittance of RTA films is higher than CFA ones where RTA@800 °C sample exhibits maximum transmittance with a sharp absorption onset. The band gap is reduced with annealing temperature and it gets decreased to a minimum of 3.19 eV for CFA@800 °C films. The samples exhibit an intense PL emission in the ultraviolet region, and the intensity of RTA films is much higher than CFA. A high decay lifetime of RTA films indicates the suppression of non-radiative decay channels.

Free Radical-Mediated Intramolecular Photocyclization of AIEgens Based on 2,3-Diphenylbenzo[b]thiophene S,S-Dioxide

As an important category of photochemical reactions, photocyclization is regarded as an ideal entry point for building intelligent photoresponsive materials. Herein, a series of aggregation-induced emission luminogens (AIEgens) with sensitive photoresponsive behavior are developed based on 2,3-diphenylbenzo[b]thiophene S,S-dioxide (DP-BTO), and the impacts of substituents with different electronic structures are investigated. The comprehensive experimental and computational characterizations reveal that their photoresponsive activity is resulted from triplet diradical-mediated intramolecular photocyclization, followed by dehydrogenation to yield stable polycyclic photoproducts. This photocyclization process is active in solution but suppressed in the solid state, and thus can act as a supplementary nonradiative decay channel for the excited state to contribute to AIE effect. Moreover, the generated triplet diradical intermediates upon light irradiation can effectively inhibit the growth of S. aureus, indicative of their promising application as antibacterial agents. This work provides an in-depth mechanistic description about the photocyclization of DP-BTO derivatives and furnishes a perspective on the correlation of photochemical decay and photophysical property.

PHOTOLUMINESCENCE PROPERTIES OF Nd3+, Yb3+ CODOPED Ga2O3 NANOPARTICLES

The availability of sensitive photon detectors and inexpensive lasers allowed us to explore more efficient fluorescent probes that will work in the second near-infrared optical window. In this study, the optical properties of Nd3+ and Yb3+ co-doped Ga2O3 nanoparticles were studied. In order to indicate the correlation between particle size, crystallinity, and optical property of present samples XRD, TEM, and Photoluminescence analyses were performed. Various excitation wavelengths and dopant concentrations were used to understand the energy transfer mechanism in Nd3+ and Yb3+ co-doped Ga2O3 nanoparticles. As the excitation wavelength increased from 325 nm to 477 and 515 nm, Yb3+ emission peak intensity decreased while Nd3+ emission peak intensity increased. This inverse relationship between the emission intensities of Yb3+ and Nd3+ ion showed the presence of energy transfer between them. The resulting emission peaks were broad and weak, indicating the presence of a non-radiative decay channel due to the crystal defects.

Photoluminescence Modulation of Ruddlesden-Popper Perovskite via Phase Distribution Regulation.

The intrinsic chaotic phase distribution in Ruddlesden-Popper Perovskite (RPP) hinders its further improvement of photoluminescence (PL) emission and limits its application in optical devices. In this work, we achieve the phase distribution regulation of RPP by varying the composition ratio of organic bulky spacer cations 1-naphthylmethylamine (NMA) and phenylethyl-ammonium (PEA), which is controllable and nondestructive for structures of RPP. By suppressing the small n-phase, the PL intensity emission of RPP is further improved. Through the time-resolved PL (TRPL) measurements, we find the PL lifetime of the sample with 66% PEA concentration increases with the temperature initially and possesses the highest values of τ1 and τ2 at ~255 K, indicating the immediate state assisting exciton radiative recombination, and it can be modulated by phase manipulation in RPP. The immediate state may outcompete other non-radiative decay channels for excited carriers, leading to the PL enhancement in RPP, and broadening its further application.

TICT compounds by design: comparison of two naphthalimide-π-dimethylaniline conjugates of different lengths and ground state geometries.

Two new twisted intramolecular charge transfer (TICT) donor-π-acceptor compounds were designed by combining a well-known electron acceptor naphthalimide unit with a classic electron donor dimethylaniline through two types of different rigid linkers. The combined steady-state and time-resolved spectroscopy of molecules in solvents of different polarities in comparison to solid-state solvation experiments of doped polymer matrixes of different polarities allowed distinguishing between solvation and conformation determined processes. The photophysical measurements revealed that non-polar solutions possess high fluorescence quantum yields of up to 70% which is a property of pre-twisted/planar molecules in the excited charge transfer (CT) states. The increase of polarity allows tuning the Stokes shift through all the visible wavelength range up to 8601 cm-1 which is accompanied by a three orders of magnitude drop of fluorescence quantum yields. This is a result of the emerged TICT states as dimethylaniline twists to a perpendicular position against the naphthalimide core. The TICT reaction of molecules enables an additional non-radiative excitation decay channel, which is not present if the twisting is forbidden in a rigid polymer matrix. Transient absorption spectroscopy was employed to visualize the excited state dynamics and to obtain the excited state reaction constants, revealing that TICT may occur from both the Franck-Condon region and the solvated pre-twisted/planar CT states. Both molecules undergo the same photophysical processes, however, a longer linker and thus a higher excited state dipole moment determines the faster excited state reactions.

Rational design of anti-Kasha photoemission from a biazulene core embedded in an antiaromatic/aromatic hybrid.

The violation of the Kasha photoemission rule in organic molecules has intrigued chemists since their discovery, being always of relevance given its connection with unique electronic properties of molecules. However, an understanding of the molecular structure-anti-Kasha property relationship in organic materials has not been well-established, possibly because of the few existing cases available, limiting their prospective exploration and ad hoc design. Here we introduce a novel strategy to design organic emitters from high excited states combining intramolecular J-coupling of anti-Kasha chromophores with the hindering of vibrationally-induced non-radiative decay channels by enforcing molecular rigidity. We apply our approach to the integration of two antiparallel azulene units bridged with one heptalene all inserted into a polycyclic conjugated hydrocarbon (PCH). With the help of quantum chemistry calculations, we identify a suitable PCH embedding structure and predict its anti-Kasha emission from the third high energy excited singlet state. Finally, steady fluorescence and transient absorption spectroscopy studies corroborate the photophysical properties in a recently synthesized chemical derivative with this pre-designed structure.

Red fluorescent benzothiadiazole derivative loaded in different nanoformulations: Optical properties and their use in bio-imaging

Fluorophores with optimized nonlinear optical properties have become prominent as contrast labels in laser scanning microscopy (LSM). The purpose of this work is to report on a novel benzothiadiazole derivative, namely 4,7-bis(5-((9,9-dioctyl-9H-fluoren-2-yl)ethynyl)thiophen-2-yl)benzo[c][1,2,5]thiadiazole (EFBT) and its optical performance when it is loaded into organic nanostructures intended as labels for LSM. Four different nanostructured labels were prepared: i) EFBT-loaded silica nanoparticles (SiNPs); ii) folate-bioconjugated SiNPs (SiNPs-FA); iii) EFBT-loaded PEGylated nanoparticles (NPs-PEG); and iv) EFBT-loaded folate-terminated PEGylated nanoparticles (NPs-PEG-FA). All these nanostructures are reported through a comparative study of their linear and nonlinear optical properties, including their performance as exogenous label agents in the cervical cancer cell line HeLa. This assessment of the performance of a specific fluorophore loaded into different nanostructured matrices (labels), and fairly compared under the same characterization conditions, including the LSM settings, is less common while previous reports had focused in comparing silica and PEGylated nanoparticles but loaded with different fluorophores. The results show that the internal molecular organization into each type of organic nanostructure impacted differently the properties of EFBT, where the silica matrix tend to preserve the optical performance of the fluorophore by preventing intermolecular interactions; in contrast, PEGylated nanoparticles favored molecular interactions and introduced non-radiative decay channels that degrades drastically the optical performance. Nevertheless, the use of functionalized ends entities produced a better cellular label uptake with PEGylated that with silica nanoparticles. In overall, the NPs-PEG-FA label produced the best HeLa imaging.