Modulated Structure Research Articles

Structural Modeling of Fluorinated Quinoxaline Core–Based Chromophores for Efficient Photovoltaic Materials: A DFT Study

ABSTRACTHerein, a series of fluorinated quinoxaline core–based chromophores (MTH1‐MTH6) with A1–π–A2–π–A1 configuration was designed by structural modulation of end‐capped acceptors in MTHR. The quantum chemical calculations were accomplished at MPW1PW91/6‐311G(d,p) functional to explore optoelectronic and photovoltaic properties of these designed compounds. The findings revealed that all the derivatives exhibited narrow band gap (Egap = 2.163–2.666 eV) with red shift spectra (610.24–766.944 eV in chloroform) as compared with MTHR. The designed compounds exhibited comparable open‐circuit voltage (Voc) and higher power conversion efficiencies (PCEs) as compared with the MTHR. Among the entitled chromophores, MTH1 was found to be a promising chromophore for organic solar cells (OSCs) owning to its lowest Egap (2.163 eV) with highest absorption peak (766.944 nm in chloroform and 717.709 nm in gaseous phase). The aforementioned findings indicate that molecular engineering of chromophores with extended acceptors enhances photovoltaic response, and this motivates researchers to develop highly effective photovoltaic devices.

Amplifying the photovoltaic properties of tetrathiafulvalenes based materials by incorporation of small acceptors: a density functional theory approach

Currently, polycyclic aromatic compounds in organic solar cells (OSCs) have gained substantial consideration in research communities due to their promising characteristics. Herein, polycyclic aromatic hydrocarbons (PAHs) core-based chromophores (TTFD1-TTFD6) were designed by structural modifications of peripheral acceptor groups into TTFR. The density functional theory (DFT) and time dependent density functional theory (TD-DFT) calculations were carried out at B3LYP/6-311G (d, p) functional to explore insights for their structural, electronic, and photonic characteristics. The structural modulation unveiled notable electronic impact on the HOMO and LUMO levels across all derivatives, leading to decreased band gaps. All the designed compounds exhibited band gap ranging from 2.246 to 1.957 eV, along with wide absorption spectra of 897.071-492.274 nm. An elevated exciton dissociation rate was observed due to the lower binding energy values (Eb = 0.381 to 0.365 eV) calculated in the derivatives compared to the reference (Eb = 0.394 eV). Furthermore, data from the transition density matrix (TDM) and density of states (DOS) also corroborated the effective charge transfer process. Comparable results of Voc for reference and designed chromophores were obtained via HOMOdonor−LUMOPC71BM. The declining Voc order values was noted as TTFD5 > TTFD6 > TTFD4 > TTFD3 > TTFD2 > TTFD1 > TTFR. Interestingly, TTFD5 was found with the smallest energy gap and highest absorption value, resulting in better charge transference among all the derivatives. The results illustrated that the modification in indenofluorene based chromophores with end-capped small acceptors proved to be a significant approach in achieving favorable photovoltaic properties.

Coupled Lattice‐Expanded Ni and MoO2 Array for Efficient Alkaline Hydrogen Evolution

AbstractTransition metal oxides have attracted much attention due to their good electrical conductivity, high chemical stability, and easy electronic structure modulation. However, it is still a great challenge to solve the problems of sluggish reaction kinetics and high overpotential in the alkaline hydrogen evolution reaction (HER) due to their poor intrinsic activity. Herein, a lattice‐expanded Ni‐decorated MoO2 array (Ni‐MoO2‐700) catalyst is prepared for the alkaline HER. Unlike most of the reported literature, the decoration of metal heteroatoms may lead to lattice expansion of the carrier catalyst. In contrast, lattice expansion of Ni is also achieved by adjusting the annealing temperature in this work. The Ni‐induced lattice‐expanding effect can not only modulate the electronic structure of the catalyst but also accelerate electron transfer during the reaction, thus increasing its intrinsic activity for the HER. As a result, Ni‐MoO2‐700 exhibits significantly enhanced catalytic activity with an overpotential of 74.9 mV at 10 mA cm−2 in 1.0 m KOH, which is far superior to that of most of the reported advanced Ni‐ and Mo‐based materials. This work provides deep intrinsic insight and a great opportunity to design efficient transition metal oxide catalysts for the alkaline HER.

Thermal properties of mullite‐type SnAlBO4 and SnGaBO4

AbstractWe report on temperature‐dependent structural and spectroscopic properties of two new members of the mullite‐type ceramics SnAlBO4 and SnGaBO4. In‐situ X‐ray powder diffraction (XRPD) demonstrates positive thermal expansion behavior for all orthorhombic lattice parameters between 13 and 840 K. The lattice thermal expansion is modeled by Grüneisen first‐order approximation, where the vibrational energy is calculated by the Debye–Einstein–anharmonicity (DEA) approach. Although the thermal changes of the metric parameters do not show any discontinuity, the double‐Debye model and low‐temperature thermal analysis leave hints for subtle displacive changes. Splitting of the tin‐doublets of the 119Sn Mössbauer spectra at low temperature is assumed to be associated with structural modulation although the temperature‐dependent Raman spectra could not support these findings. The modulation could either be dynamic which requires much longer thermal equilibration than the speed of the data collection for XRPD and Raman spectroscopy. Selective Raman mode frequencies are analyzed using a modified Klemens model, which helps to understand the thermal anharmonic behaviors of the SnO4, MO6, and BO3 polyhedra as a function of temperature.

Lacticaseibacillus paracasei 207-27 alters the microbiota-gut-brain axis to improve wearable device-measured sleep duration in healthy adults: a randomized, double-blind, placebo-controlled trial.

Objective: Probiotics have been reported to exert beneficial effects on sleep through the gut-brain axis. Therefore, this randomized, double-blind, placebo-controlled trial assessed the effects of Lacticaseibacillus paracasei 207-27 supplementation on sleep quality and its safety and potential mechanisms. Method and study design: Healthy adults under mild stress aged 18-35 years consumed low or high doses of L. paracasei 207-27 or a placebo for 28 days. Fecal samples, blood samples, and questionnaires were collected at the baseline and the end of the intervention. Sleep quality was measured using wearable devices and Pittsburgh sleep quality index (PSQI) questionnaire. Serum inflammatory markers, corticotropin-releasing hormone, adrenocorticotropic hormone (ACTH), cortisol (COR), γ-aminobutyric acid, and 5-hydroxytryptamine levels were detected using enzyme-linked immunosorbent assay. The gut microbiota was analyzed using 16S rRNA sequencing and bioinformatics. Short-chain fatty acids levels were detected using gas chromatography-mass spectrometry. Results: Both the low-dose and high-dose groups exhibited significant improvements in wearable device- measured sleep duration compared to the placebo group. The global scores of PSQI in three groups significantly decreased after intervention without statistical difference between groups. At the phylum level, the low-dose group exhibited a higher relative abundance of Bacteroidota and a lower Firmicutes-to-Bacteroidetes (F/B) ratio. At the genus level, two treatment groups had higher relative abundance of Bacteroides and Megamonas, alongside lower levels of Escherichia-Shigella. Furthermore, the low-dose group exhibited significant increases in acetic acid, propionic acid, butyric acid, and valeric acid levels, while two treatment groups exhibited a significant decrease in COR levels. Correlation analysis revealed that the increased levels of acetic acid and butyric acid in the low-dose group may be associated with decreased ACTH. Conclusion: L. paracasei 207-27 administration in healthy adults resulted in improvements in gut microbiota community and sleep duration. The mechanisms might involve modulation of the gut microbiota structure to regulate the function of the gut-brain axis, including increases in SCFA levels and decreases in hypothalamic-pituitary-adrenal axis activity. The Chinese clinical trial registry number is ChiCTR2300069453 (https://www.chictr.org.cn/showproj.html?proj=191193, registered 16 May 2023 - retrospectively registered).

Genome engineering of materials based on Ce doping, high-performance electromagnetic wave absorber for marine environment

Traditional microwave absorbing materials (MAM) are difficult to meet the current increasingly complex electromagnetic environment, MAM began to functionally integrated development to meet the needs of diversified applications. For the high humidity and high salt spray environment of the ocean, the development of electromagnetic absorber integrating microwave absorption (MA) and corrosion protection functions is imminent. In this work, high-quality genes were screened through materials genome engineering, and in-situ doping strategies of Ce gene were designed to synergistically enhance MA properties using composition modulation and structure modulation, the effective absorption bandwidth (EAB) of composite material WC@FCC1 can reach 5.62 GHz at an ultra-thin thickness of 1.66 mm. Thanks to the unique 4f orbital mechanism of Ce element, CeO2 is endowed with excellent redox property, forming an oxide protective film on the surface, which prevents the entry of external corrosive media. The excellent corrosion protection performance of the composite material has been verified through electrochemical testing and molecular dynamics simulation. This work provides new design ideas for high-performance MAM, as well as new strategies and insights for functionally integrated electromagnetic absorber.

Atomically dispersed iron sites from eco-friendly microbial mycelium as highly efficient hydrogenation catalyst

Iron, one of the most abundant elements on earth and an essential element for living organisms, plays a crucial role in our daily metabolism. In the field of catalysis, the development of high-performance catalysts based on less toxic iron element is also of significant importance for green chemistry and a sustainable future. To construct Fe-based heterogeneous catalysts with excellent hydrogenation performance, precise modulation of the atomic coordination structure is a key strategy for enhancing catalytic activity. In this study, we present an in-situ coating method for applying a zeolitic imidazolate framework (ZIF) onto the surface of fungal hyphae. The asymmetric coordination structure of Fe1-N3P1 was precisely tailored by utilizing the phosphorus source from the fungus and the nitrogen source in the ZIFs. Detailed characterizations and density functional theory calculations revealed that the incorporation of ZIFs not only increased the specific surface area of catalysts, but also facilitated the dispersion of Fe2P nanoparticles into the Fe1-N3P1 center, making the lowest reaction energy barrier and resulting in the best performance for nitrobenzene hydrogenation when compared to the Fe2P nanoparticles and clusters. This research introduces a novel design concept for constructing asymmetric monoatomic configuration based on the inherent characteristics of natural microorganisms and the exogenous porous coordination polymers.

Cracking Mechanism and Inhibition Strategies of Polycrystalline NCM Electrode Particles.

Developing a high-energy-density cathode material (LiNi1-x-yCoxMnyO2, NCM) for lithium-ion batteries is crucial to the electric vehicle and energy storage industries. However, the continuous insertion/extraction of Li+ generates diffusion-induced stress, causing NCM particles to crack or even pulverize, leading to battery capacity loss and limiting its wider commercial application. Current experimental studies are primarily postmortem examinations, and it is difficult to capture the particle cracking evolution. Simulation studies frequently ignore or simplify anisotropic volume contraction, demonstrating an insufficient understanding of the cracking mechanism of NCM polycrystalline particles, and cracking prevention strategies still need improvement. Therefore, we develop an anisotropic polycrystalline fracture phase-field model (AP-FPFM) that focuses on the anisotropic volume contraction of primary particles and precisely generates grain boundary distribution, coupling with Li+ diffusion, mechanical stress, and particle cracking. We employ AP-FPFM to demonstrate the behavior and mechanism of NCM polycrystalline particle cracking and illustrate the necessity and importance of anisotropic volume contraction to understand particle cracking. Furthermore, we explore the effects of average primary particle size, secondary particle size, and core-shell structure modulation on crack initiation and propagation and propose strategies to inhibit or migrate NCM polycrystalline particle cracking. This work provides theoretical support for revealing the cracking mechanism of anisotropic polycrystalline NCM particles and supplying optimization strategies to suppress particle cracking and improve the mechanical stability.

Crystal structure of the incommensurate modulated high-pressure phase of the potassium guaninate monohydrate.

The crystal structure of the incommensurate modulated phase of potassium guaninate monohydrate has been solved on the basis of high-pressure single-crystal X-ray diffraction data. The modulated structure was described as a `mosaic' sequence of three different local configurations of two neighbouring guaninate rings. In contrast to known examples of incommensurate modulated organic compounds, the modulation functions of all atoms are discontinuous. This is the first example of the experimental detection of an incommensurate modulated crystal structure that can be modelled using the special `soliton mode' modulation function proposed by Aramburu et al. [(1995), J. Phys. Condens. Matter, 7, 6187-6196].

Wave patterns of the coupled nonlinear Schrödinger equations in photonic crystal fibers with four-wave mixing

Abstract In this paper, we examine the behavior of modulation instability within photonic crystals. The model employed is the coherent coupled nonlinear Schrödinger equation, incorporating weak birefringence and four-wave mixing, which arises at the edge of the optical mode. The linear analysis is used to derive the modulation instability spectrum. Throughout the modulation instability spectrum, we identify both stable and unstable modes, thereby confirming the breakdown of the plane wave. For certain four-wave mixing parameters, the amplitude of the modulation instability spectrum and its bandwidths expand, creating an opening for localized structures to emerge. Another aspect of this study has been demonstrated in normal and anomalous dispersion regimes where an increasing initial amplitude of the plane wave is fulfilled. Specifically, numerical simulations highlight the occurrence of Benjamin-Feir instability, where wave patterns emerge under the influence of four-wave mixing. Additionally, solitonic waves are generated, demonstrating the presence of Akhmediev breathers and other modulated structures, confirming that photonic crystals with four-wave mixing are conducive to these formations. The findings from this study could inform future research in the development of nonlinear photonic waveguides.

Structural modulation of graphene–polyimide interfaces below pyrolysis temperature under electrothermal treatment

Structural modulation of graphene–polyimide interfaces below pyrolysis temperature under electrothermal treatment

Electron Migratory Polarization of Interfacial Electric Fields Facilitates Efficient Microwave Absorption

AbstractHigh‐performance microwave absorption materials (MAM) are often accompanied by synergistic effects of multiple loss mechanisms, but the contribution share of various loss mechanisms has been neglected to provide a template and reference for the design of MAM. Here, a highly conductive 2D structure is designed through a functional group‐induced structure modulation strategy, composite L‐Ni@C can reach an effective absorption bandwidth of 6.45 GHz at 15% fill rate, with a maximum absorption efficiency of 99.9999%. Through the layer‐by‐layer analysis of the loss mechanism, it is found that the strong loss originates from the polarization loss at the heterogeneous interface. The movement of space charge between the two‐phase interface forms an interfacial electric field, and the in situ doping of nitrogen is cleverly achieved by the introduction of amino functional groups, which significantly enhances the rate of space charge transfer between the two‐phase interface and greatly facilitates the electron migration polarization. The space charge motion law of the interfacial electric field is also simulated using COMSOL simulation software to illustrate the electron migration polarization mechanism at heterogeneous interfaces. This work fills the gap of functional group‐induced structural modulation and presents new theories into the mechanism of space charge movement at heterogeneous interfaces.

Intriguing astrocyte responses in CA1 to reduced and rehabilitated masticatory function: Dorsal and ventral distinct perspectives in adult mice

ObjectiveWe sought to investigate the plasticity of diet-induced changes in astrocyte morphology of stratum lacunosum-moleculare (SLM) in CA1. DesignThree diet regimes were adopted in 15 mice, from the 21st postnatal day to 6 months. The first diet regimen was pellet feed, called Hard Diet (HD). The second, with reduced masticatory, received a pellet-diet followed by a powdered-diet, and it was identified as Hard Diet/Soft Diet (HD/SD). Finally, the group with rehabilitated masticatory was named Hard Diet/Soft Diet/Hard Diet (HD/SD/HD). In the end, euthanasia and brain histological processing were performed, in which astrocytic immunoreactivity to glial-fibrillary-acidic-protein (GFAP) was tested. In reconstructed astrocytes, morphometric analysis was performed. ResultsAstrocyte morphometric revealed that changes in masticatory regimens impact astrocyte morphology. In the dorsal CA1, switching from a hard diet to a soft diet led to reductions in most variables, whereas in the ventral, fewer variables were affected, highlighting regional differences in astrocyte responses. Cluster analysis further showed that diet-induced changes in astrocyte morphology were reversible in the dorsal region, but not in the ventral region, indicating a persistent impact on astrocyte diversity and complexity in the ventral even after rehabilitation. Correlation tests between astrocyte morphology and behavioral performance demonstrated disrupted relationships under masticatory stress, with effects persisting after rehabilitation. ConclusionChanges in the diet result in significant alterations in astrocyte morphology, suggesting a direct link between dietary modulation and cellular structure. Morphometric analyses revealed distinct alterations in astrocyte morphology in response to changes in the masticatory regimen, with both dorsal/ventral regions displaying notable changes. Moreover, the regional differential effects on astrocytes underscore the complexity of mastication on neuroplasticity and cognitive function.

Tuning architectural synergy reactivity of nano-tin oxide on high storage reversible capacity retention of ammonium vanadate nanobelt array cathode for lithium-ion battery

Enabling ambient cycling stability of vanadium-based materials is of fundamental importance in the advancement of next generation electrodes for high-performance lithium-ion batteries. Although, extending these host layered nano-architectures illustrate the effective electrochemical activity by regulating the gallery space for fast Li+ storage, the reported structural integrity in terms of the cycling stability for vanadium-based cathodes is highly challenging. In present study, a series of NH4V4O10-SnO2 (NHV-SnO2) nanocomposite consisting of diverse contents of SnO2 (x: 5.0, 15.0 and 30.0 wt%) were synthesized through a three-step program based on sonochemical-calcination-hydrothermal treatment and employed as an advanced energetic material for lithium-ion battery cathodes. For the first time, understanding the impact of SnO2 loading on electrochemical reactions of NHV-based electrodes was regarded as an effective engineering strategy to optimize structural modulation and cell lifetime without distinct capacity fading. Notably, combination of NHV and SnO2 in optimum proportions not only enhances the specific surface area, but also expand buffer the volume change for lithium-ion intercalation/extraction. By this design, the assembled battery containing 15.0 wt% SnO2 illustrated stable capacities of 301.77 mAh g−1 (30 mA g−1) and 232.05 mAh g−1 (240 mA g−1) with capacity retention values as high as 97.94 % and 97.03 % for 50 cycles, respectively. Of note, the results described here could show a vital guidance toward designing better composite-based cathode material for energy storage devices.

Structural modulation in colored polymer bands of methacrylic acid-based frontal polymerization

The periodic colored polymer bands have been investigated in frontal polymerization (FP) reaction containing methacrylic acid (MAA), hydroquinone, Benzoyl peroxide (BP), and N, N Dimethyl aniline (DMA) system. The MAA acts as a monomer, which was diluted adequately with methanol (MeOH), ethanol (EtOH), and butanol (BuOH) separately to observe the patterning characteristics in different reaction schemes. The structural modulations that include the periodicity of colored polymer bands, morphological changes, and spacings between two adjacent layers were studied. The colored variations of polymer bands and their dependency on the concentration of BP, hydroquinone and alcoholic compositions have been studied. The highly consistent pink-white colored polymer bands, loosely-packed band structures, and perfectly ordered band structures resulted in MeOH, EtOH, and BuOH systems, respectively, as discussed. The evolution of tiny bubbles and convection-type instability has been observed in different conditions of the FP reactions that significantly affect the planar movement of the polymer fronts. The hot spots, which usually represent the high-temperature regions of a typical frontal surface, have also been demonstrated in all reacting systems, which may cause spin mode propagation of the fronts and change the surface geometry, as described. The materials characterization was carried out using UV-visible spectrophotometer, NMR, FTIR, and FESEM techniques, providing information about the polymer phases involved in band structures, composition, and surface properties. The analytical data and results obtained during the study further emphasized that two different coloured polymers, namely 1, 4-dihydroxy anthraquinone methacrylic acid and poly-methacrylic acid dihydroxy, anthraquinone produced simultaneously and crystallized periodically, results in the development of a coloured polymer band structures. The possible reactions and associated chemical mechanisms concerning the observations, the nature of the monomer, and solvent characteristics have been proposed, which show a close agreement with the analytical data and results obtained during the study

Reviving Sodium Tunnel Oxide Cathodes Based on Structural Modulation and Sodium Compensation Strategy Toward Practical Sodium-Ion Cylindrical Battery.

As a typical tunnel oxide, Na0.44MnO2 features excellent electrochemical performance and outstanding structural stability, making it a promising cathode for sodium-ion batteries (SIBs). However, it suffers from undesirable challenges such as surface residual alkali, multiple voltage plateaus, and low initial charge specific capacity. Herein, an internal and external synergistic modulation strategy is adopted by replacing part of the Mn with Ti to optimize the bulk phase and construct a Ti-containing epitaxial stabilization layer, resulting in reduced surface residual alkali, excellent Na+ transport kinetics and improved water/air stability. Specifically, the Na0.44Mn0.85Ti0.15O2 using water-soluble carboxymethyl cellulose as a binder can realize a capacity retention rate of 94.30% after 1,000 cycles at 2C, and excellent stability is further verified in kilogram large-up applications. In addition, taking advantage of the rich Na content in Prussian blue analog (PBA), PBA-Na0.44Mn1-xTixO2 composites are designed to compensate for the insufficient Na in the tunnel oxide and are matched with hard carbon to achieve the preparation of coin full cell and 18650 cylindrical battery with satisfactory electrochemical performance. This work enables the application of tunnel oxides cathode for SIBs in 18650 cylindrical batteries for the first time and promotes the commercialization of SIBs.

Strategically Modulating Proton Activity and Electric Double Layer Adsorption for Innovative All-Vanadium Aqueous Mn2+/Proton Hybrid Batteries.

Aqueous Mn-ion batteries (MIBs) exhibit a promising development potential due to their cost-effectiveness, high safety, and potential for high energy density. However, the development of MIBs is hindered by the lack of electrode materials capable of storing Mn2+ ions due to acidic manganese salt electrolytes and large ion radius. Herein, the tunnel-type structure of monoclinic VO2 nanorods to effectively store Mn2+ ions via a reversible (de)insertion chemistry for the first time is reported. Utilizing exhaustive in situ/ex situ multi-scale characterization techniques and theoretical calculations, the co-insertion process of Mn2+/proton is revealed, elucidating the capacity decay mechanism wherein high proton activity leads to irreversible dissolution loss of vanadium species. Further, the Grotthuss transfer mechanism of protons is broken via a hydrogen bond reconstruction strategy while achieving the modulation of the electric double-layer structure, which effectively suppresses the electrode interface proton activity. Consequently, the VO2 demonstrates excellent electrochemical performance at both ambient temperatures and -20°C, especially maintaining a high capacity of 162mAhg-1 at 5Ag-1 after a record-breaking 20000 cycles. Notably, the all-vanadium symmetric pouch cells are successfully assembled for the first time based on the "rocking-chair" Mn2+/proton hybrid mechanism, demonstrating the practical application potential.

Eco-friendly and facile nanomanufacturing of amorphous Co-Ce-Fe trimetallic molybdates composites for accelerated anodic oxygen evolution in alkaline water electrolysis: Evaluation of active sites performance

Currently, endeavors to scale up the production of amorphous catalysts are still impeded by intricate synthesis conditions. Here, we have prepared a series of metal-based molybdate via one-step coprecipitation method. After ingredient optimization, amorphous Co2CeFe2-MoO4 was identified as exhibiting the highest intrinsic activity among its counterparts. Modulation of electron structure enables Co2CeFe2-MoO4 to balance the adsorption behavior towards reactive intermediates. Ultimately, the obtained Co2CeFe2-MoO4 molybdate demonstrated a captivating OER performance, showcasing a low overpotential of 230 mV at 10 mA cm-2. Moreover, the alkaline electrolyzer employing the Co2CeFe2-MoO4 anode exhibited a low cell voltage of 1.50 V for water splitting and underwent an acceptable attenuation of 4.99% after 165 hours of continuous operation, demonstrating its favorable catalytic activity and durability. This work provides a facile and eco-friendly synthesis pathway for crafting cost-effective and durable earth-abundant OER electrocatalysts tailored for water splitting to produce clean hydrogen.

Na-doped nitride-rich carbon nitride for efficient photocatalytic NO abatement

Nitride-rich carbon nitride (C3N5) is gaining prominence as a substantial catalyst for photocatalytic reaction because of its narrow bandgap, extensive light responsiveness, and photocatalytic stability. To enhance the efficiency of photogenerated carrier separation in C3N5, we propose a strategy for Na-doped modification. Photocatalytic NO removal efficiency of C3N5/Na achieved 73.9 % under 15 % relative humidity, which is 3.5 times higher than that of C3N5. Besides, the NO removal efficiency of C3N5/Na maintained above 70 % even after six cycles under different relative humidities. Detailed analytical characterization revealed that Na doping of C3N5 not only increased its specific surface area by 5.5-fold but also modulated its energy band structure and molecular structure, leading to improved hole-carrier separation efficiency and enhancing the photocatalytic performance of C3N5/Na. ESR and reactive species trapping experiments confirmed that electrons and superoxide are the main reactive species, and modulation of the energy band structure accelerates the reaction. This work explains the effect of Na doping on C3N5 and provides a new strategy for designing efficient for photocatalytic treatment of air pollution.

Improving the Lithography Sensitivity of Atomically Precise Tin-Oxo Nanoclusters via Heterometal Strategy.

Tin-oxo clusters are increasingly recognized as promising materials for nanolithography technology due to their unique properties, yet their structural impacts on lithography performance remain underexplored. This work explores the structural impacts of heterometal strategies on the performance of tin-oxo clusters in nanolithography, focusing on various metal dopants and their coordination geometries. Specifically, SnOC-1(In), SnOC-1(Al), SnOC-1(Fe), and SnOC-2 were synthesized and characterized. These clusters demonstrate excellent solubility, dispersibility, and stability, facilitating the preparation of high-quality films via spin-coating for lithographic applications. Notably, this work innovatively employs nano-infrared (nano-IR), neutron reflectivity (NR), and X-ray reflectivity (XRR) measurements to confirm film homogeneity. Upon electron beam lithography (EBL), all four materials achieve 50 nm line patterns, with SnOC-1(In) demonstrating the highest lithography sensitivity. This enhanced sensitivity is attributed to indium dopants, which possess superior EUV absorption capabilities and unsaturated coordination environments. Further studies on exposure mechanisms indicated that Sn-C bond cleavage generates butyl free radicals, promoting network formations that induce solubility-switching behaviors for lithography. These findings underscore the efficacy of tailored structural design and modulation of cluster materials through heterometal strategies in enhancing lithography performance, offering valuable insights for future material design and applications.