Thermally Activated Photoluminescence Induced by Tunable Interlayer Interactions in Naturally Occurring van der Waals Superlattice SnS/TiS2.

van der Waals (vdW) superlattices, comprising different 2D materials aligned alternately by weak interlayer interactions, offer versatile structures for the fabrication of novel semiconductor devices. Despite their potential, the precise control of optoelectronic properties with interlayer interactions remains challenging. Here, we investigate the discrepancies between the SnS/TiS2 superlattice (SnTiS3) and its subsystems by comprehensive characterization and DFT calculations. The disappearance of certain Raman modes suggests that the interactions alter the SnS subsystem structure. Specifically, such structural changes transform the band structure from indirect to direct band gap, causing a strong PL emission (∼2.18 eV) in SnTiS3. In addition, the modulation of the optoelectronic properties ultimately leads to the unique phenomenon of thermally activated photoluminescence. This phenomenon is attributed to the inhibition of charge transfer induced by tunable intralayer strains. Our findings extend the understanding of the mechanism of interlayer interactions in van der Waals superlattices and provide insights into the design of high-temperature optoelectronic devices.

Tailoring Broadband Nonlinear Optical Characteristics and Ultrafast Photocarrier Dynamics of Bi2O2S Nanosheets by Defect Engineering.

Low-dimensional bismuth oxychalcogenides have shown promising potential in optoelectronics due to their high stability, photoresponse, and carrier mobility. However, the relevant studies on deep understanding for Bi2O2S is quite limited. Here, comprehensive experimental and computational investigations are conducted in the regulated band structure, nonlinear optical (NLO) characteristics, and carrier dynamics of Bi2O2S nanosheets via defect engineering, taking O vacancy (OV) and substitutional Se doping as examples. As the OV continuously increased to ≈35%, the optical bandgaps progressively narrow from ≈1.21 to ≈0.81 eV and NLO wavelengths are extended to near-infrared regions with enhanced saturable absorption. Simultaneously, the relaxation processes are effectively accelerated from tens of picoseconds to several picoseconds, as the generated defect energy levels can serve as both additional absorption cross-sections and fast relaxation channels supported by theoretical calculations. Furthermore, substitutional Se doping in Bi2O2S nanosheets also modulate their optical properties with the similar trends. As a proof-of-concept, passively mode-locked pulsed lasers in the ≈1.0 µm based on the defect-rich samples (≈35% OV and ≈50% Se-doping) exhibit excellent performance. This work deepens the insight of defect functions on optical properties of Bi2O2S nanosheets and provides new avenues for designing advanced photonic devices based on low-dimensional bismuth oxychalcogenides.

Strain-Dependent Band Splitting and Spin-Flip Dynamics in Monolayer WS2.

Triggered by the expanding demands of semiconductor devices, strain engineering of two-dimensional transition metal dichalcogenides (TMDs) has garnered considerable research interest. Through steady-state measurements, strain has been proved in terms of its modulation of electronic energy bands and optoelectronic properties in TMDs. However, the influence of strain on the spin-orbit coupling as well as its related valley excitonic dynamics remains elusive. Here, we demonstrate the effect of strain on the excitonic dynamics of monolayer WS2 via steady-state fluorescence and transient absorption spectroscopy. Combined with theoretical calculations, we found that tensile strain can reduce the spin-splitting value of the conduction band and lead to transitions between different exciton states via spin-flip mechanism. Our findings suggest that the spin-flip process is strain-dependent, provides a reference for application of valleytronic devices, where tensile strain is usually existing during their design and fabrication.

Design, Synthesis, and Ultrafast Carrier Dynamics of Core-Substituted Naphthalene Diimide-Based Covalent Organic Frameworks.

A series of two-dimensional polyimide covalent organic frameworks (2D COF) based on core-substituted naphthalene diimides (cNDIs) were designed and synthesized with the characteristic of tunable bandgap without global structural changes. Cyclic voltammetry (CV) and DFT calculations indicated that COFcNDI-OEt and COFcNDI-SEt possess higher HOMO/LUMO levels and narrower bandgaps than COFNDI-H. Further investigation indicated that the COF bandgaps are not only related to the electron-donating substituents but also varied with respect to the interlayer distances. Moreover, the femtosecond transient absorption (TA) spectra manifested that the electron donor substituents are beneficial to the charge delocalization in the π-columnar unit, resulting in a longer lifetime of charge recombination, which is one of the pivotal prerequisites for high-performance solar cells and photocatalysis.

Unveiling the energy transfer mechanism between aqueous colloidal NIR-II quantum dots and water.

Hydrophilic semiconductor quantum dots (QDs) with emission in the second near-infrared window (NIR-II) have been widely studied in bioimaging applications. In such cases, QDs are usually dispersed in water. As is known, water has strong absorbance in the NIR-II region. However, investigations on the interaction between NIR-II emitters and water molecules are ignored in previous studies. Herein, we synthesized a series of mercaptoundecanoic acid-coated silver sulfide (Ag2S/MUA) QDs with various emissions that partially or completely overlapped with the absorbance of water at 1200 nm. By constructing a hydrophobic interface of cetyltrimethylammonium bromide (CTAB) with MUA on the Ag2S QDs surface via forming an ionic bond, significant enhancement of Ag2S QDs photoluminescence (PL) intensity was observed, as well as a prolonged lifetime. These findings suggest that there is an energy transfer between Ag2S QDs and water in addition to the classical resonance absorption. Transient absorption and fluorescence spectra results revealed that the increased PL intensities and lifetime of Ag2S QDs originated from the suppressed energy transfer from Ag2S QDs to the water due to the CTAB bridged hydrophobic interfaces. This discovery is important for a deeper understanding of the photophysical mechanisms of QDs and their applications.

Reticular Synthesis of One-Dimensional Covalent Organic Frameworks with 4-c sql Topology for Enhanced Fluorescence Emission.

Covalent organic frameworks (COFs) have been extensively investigated due to their unique structure, porosity, and functionality. However, at the topological level, COFs remain as two-dimensional (2D) or three-dimensional (3D) structures, while COFs with one-dimensional (1D) topology have not been systematically explored. In this work, we proposed a synthetic strategy for the construction of 1D-COFs based on non-linear edges and suitable high-symmetry vertices. Compared with their 2D-COFs counterparts, the 1D-COFs with AIEgens located at the vertex of the frame exhibited enhanced fluorescence. The density functional theory (DFT) calculations revealed that the dimensional-induced rotation restriction (DIRR) effect could spontaneously introduce additional non-covalent interactions between the strip frames, which could substantially diminish non-radiative transitions. This work also provides protocols for the design of 1D-COFs and a guidance scheme for the synthesis of emitting COFs.

Rapid and Large-Scale Quality Assessment of Two-Dimensional MoS2 Using Sulfur Particles with Optical Visualization.

The efficient nondestructive assessment of quality and homogeneity for two-dimensional (2D) MoS2 is critically important to advance their practical applications. Here, we presented a rapid and large-area assessment method for visually evaluating the quality and uniformity of chemical vapor deposition (CVD)-grown MoS2 monolayers simply with conventional optical microscopes. This was achieved through one-pot adsorbing abundant sulfur particles selectively onto as-grown poorer-quality MoS2 monolayers in a CVD system without any additional treatment. We further revealed that this favorable adsorption of sulfur particles on MoS2 originated from their intrinsic higher-density sulfur vacancies. Based on unadsorbed MoS2 monolayers, superior performance field effect transistors with a mobility of ∼49 cm2 V-1 s-1 were constructed. Importantly, the assessment approach was noninvasive due to the all-vapor-phase and moderate adsorption-desorption process. Our work offers a new route for the performance and yield optimization of devices by quality assessment of 2D semiconductors prior to device fabrication.

Layer-Tunable Nonlinear Optical Characteristics and Photocarrier Dynamics of 2D PdSe2 in Broadband Spectra.

Layered 2D transition metal dichalcogenides (TMDCs) exhibited fascinating nonlinear optical (NLO) properties for constructing varied promising optoelectronics. However, exploring the desired 2D materials with both superior nonlinear absorption and ultrafast response in broadband spectra remain the key challenges to harvest their greatest potential. Here, based on synthesizing 2D PdSe2 films with the controlled layer number, the authors systematically demonstrated the broadband giant NLO performance and ultrafast excited carrier dynamics of this emerging material under femtosecond visible-to-near-infrared laser-pulse excitation (400-1550 nm). Layer-dependent and wavelength-dependent evolution of optical bandgap, nonlinear absorption, and photocarrier dynamics in the obtained 2D PdSe2 are clearly revealed. Specially, the transition from semiconducting to semimetallic PdSe2 induced dramatic changes of their interband absorption-relaxation process. This work makes 2D PdSe2 more competitive for future ultrafast photonics and also opens up a new avenue for the optical performance optimization of various 2D materials by rational design of these materials.

Hierarchical Multicavity Nitrogen-Doped Carbon Nanospheres as Efficient Polyselenide Reservoir for Fast and Long-Life Sodium-Selenium Batteries.

Sodium-selenium (Na-Se) battery has been emerging as one of the most prospective energy storage systems owing to their high volumetric energy density and cost effectiveness. Nevertheless, the shuttle effect of sodium polyselenide (NaPSe) and sluggish electrochemical reaction kinetics present the main bottlenecks for its practical implementation. Herein, a new Se host of 3D nitrogen-doped hierarchical multicavity carbon nanospheres (3D NHMCs) is designed and synthesized via a facile self-sacrifice templating strategy. The 3D NHMCs are verified to hold a favorable structure of a hollow macropore core and numerous micro/mesopores hollow shell for hosting Se, which can not only maximize Se utilization and alleviate the volumetric expansion but also promote the electrical/ionic conductivity and electrolyte infiltration. Moreover, the abundant self-functionalized surfaces as an efficient NaPSe scavenger via robust physical-chemical dual blocking effects demonstrate high-efficiency in situ anchoring-diffusion-conversion of NaPSe, rendering rapid reaction kinetics and remarkable suppressive shuttle effect, as evidenced by systematic experimental analysis and density functional theory calculations. As a result, the high-Se-loading 3D NHMCs/Se cathode exhibits an ultrahigh volumetric capacity (863 mAh cm-3 ) and rate capability (377 mAh g-1 at 20 C) and unexceptionable stability over 2000 cycles at 2 C.

Hydrazone-Linked Heptazine Polymeric Carbon Nitrides for Synergistic Visible-Light-Driven Catalysis.

Heptazine-based conjugated polymeric carbon nitrides (PCNs) are promising metal-free photocatalysts, yet their synthesis is challenging due to the electron-deficiency and insolubility of heptazine units. Indeed, heptazine-containing polymers have only been prepared through nucleophilic substitution with amines by using toxic cyameluric chloride as the starting material. Herein, we report the novel and environmentally friendly method for preparing heptazine-based mesoporous PCNs with hydrazone links formed through a simple Schiff base condensation of melem-NH2 and aldehydes. Unlike cyameluric chloride, melem-NH2 is non-toxic, stable, and can be readily obtained from melem and hydrazine in solution. We demonstrate that the hydrazone linkages and the heptazine units synergistically enhance the photocatalytic activity of PCNs in visible-light-driven aerobic oxidation of benzyl alcohol to benzaldehyde. In particular, the polymer constructed from melem-NH2 and p-phthalaldehyde shows 17 times more activity than graphitic carbon nitride (g-C3 N4 ).

MOF-Derived Hybrid Hollow Submicrospheres of Nitrogen-Doped Carbon-Encapsulated Bimetallic Ni-Co-S Nanoparticles for Supercapacitors and Lithium Ion Batteries.

The development of bimetallic transition-metal sulfide and nitrogen-doped carbon composites with unique hollow structure is highly desirable for energy storage applications but is also challenging. In the present work, we demonstrate a facile metal-organic framework engaged strategy for synthesizing bimetallic nickel cobalt sulfide and nitrogen-doped carbon composites with hollow spherical structure (denoted as hollow Ni-Co-S- n/NC composites) and a Ni/Co molar ratio ( n value) that can be easily controlled. When evaluated as electrode materials for both supercapacitors and lithium ion batteries, it is found that the hollow Ni-Co-S-0.5/NC composite with a Ni/Co molar ratio of 0.5 exhibits optimal electrochemical performance. The hollow Ni-Co-S-0.5/NC composite exhibits a high specific capacity of 543.9 C g-1 at 1 A g-1 and maintains a capacity retention of 67.3% when the current density is increased to 20 A g-1. An asymmetric supercapacitor based on the hollow Ni-Co-S-0.5/NC composite is fabricated, which shows good electrochemical performance with a high energy density of 39.6 W h kg-1 at a power density of 808 W kg-1. For lithium storage, the hollow Ni-Co-S-0.5/NC composite manifests a high reversible discharge capacity of 755.0 mA h g-1 at 200 mA g-1 for 200 cycles as well as good rate capability. The excellent electrochemical performance could be attributed to the desirable structural, compositional, and component advantages. This work could offer new insight into the rational design and synthesis of highly efficient electrode materials for both supercapacitors and lithium ion batteries.

Resorcinol-Formaldehyde Resin-Coated Prussian Blue Core-Shell Spheres and Their Derived Unique Yolk-Shell FeS2@C Spheres for Lithium-Ion Batteries.

The practical applications of transition metal sulfides as electrode materials for lithium-ion batteries (LIBs) is greatly hindered by the fast capacity fading owing to the large volume expansion. To address this issue, construction of transition metal sulfide and carbon nanocomposites with unique yolk-shell structures is an effective strategy but also remains a great challenge. In this work, we reported a facile approach to synthesize the unique yolk-shell FeS2@carbon (FeS2@C) spheres via calcination treatment of the resorcinol-formaldehyde (RF) resin-coated Prussian blue (FeFe PB) core-shell spheres in Ar atmosphere and a subsequent sulfidation treatment. The synthetic method herein was quite simple and convenient. Such unique structure design could effectively prevent the large volume expansion and dissolution of the active materials in the electrolytes during lithiation. As expected, the yolk-shell FeS2@C spheres exhibited good electrochemical performance as anode materials for LIBs, which displayed a high discharge capacity of 560 mA h g-1 at 100 mA g-1 for 100 cycles. When the current density increased to 1000 mA g-1, a reversible discharge capacity of 269 mA h g-1 was still retained after 500 cycles. The present work demonstrated an extraordinary synthetic strategy to construct transition metal sulfide and carbon nanocomposites with unique yolk-shell structure. In addition, this RF resin coating strategy can be further extended to synthesize other RF resin-coated PB analogue (PBA) core-shell nanostructures, demonstrating the generality of this RF resin coating strategy.

Light-Induced Reversible Self-Assembly of Gold Nanoparticles Surface-Immobilized with Coumarin Ligands.

A novel light-induced reversible self-assembly (LIRSA) system is based on the reversible photodimerization and photocleavage of coumarin groups on the surface of gold nanoparticles (AuNPs) in THF solution. Facilitated by coumarin groups, light irradiation at 365 nm triggers the stable assembly of monodisperse AuNPs; the resulting self-assembly system can be disassembled back to the disassembled state by a relatively short exposure to benign UV light. The reversible self-assembly cycle can be repeated 4 times. A specific concentration range of coumarin ligand and the THF solvent were identified to be the two predominant factors that contribute to the LIRSA of AuNPs. This is the first successful application of reversible photodimerization based on a coumarin derivative in the field of AuNP LIRSA. This LIRSA system may provide unique opportunities for the photoregulated synthesis of many adjustable nanostructures and devices.

CdS nanobubbles and Cd-DMS nanosheets: solvothermal synthesis and formation mechanism.

CdS nanobubbles and Cd-DMS nanosheets have been prepared by a solvothermal method from a solution of Cd2+ in dimethyl sulfoxide in the absence of elemental S. A formation mechanism for the nanobubble morphology arising during the CdS nanocrystal growth has been proposed, based on the results of transmission electron microscopy and photoluminescence spectrophotometry. The correlation of the morphology with reaction time was also suggested, and may be applicable to the solvothermal synthesis of other nanomaterials.

Confined WS2 Nanosheets Tubular Nanohybrid as High-Kinetic and Durable Anode for Sodium-Based Dual Ion Batteries.

Sodium based dual-ion battery (SDIB) has been regarded as one of the promising batteries technologies thanks to its high working voltage and natural abundance of sodium source, its practical application yet faces critical issues of low capacity and sluggish kinetics of intercalation-type graphite anode. Here, a tubular nanohybrid composed of building blocks of carbon-film wrapped WS2 nanosheets on carbon nanotube (WS2 /C@CNTs) was reported. The expanded (002) interlayer and dual-carbon confined structure endowed WS2 nanosheets with fast charge transportation and excellent structural stability, and thus WS2 /C@CNTs showed highly attractive electrochemical properties for Na+ storage with high reversible capacity, fast kinetic, and robust durability. The full sodium-based dual ion batteries by coupling WS2 /C@CNTs anode with graphite cathode full cell presented a high reversible capacity (210 mAh g-1 at 0.1 A g-1 ), and excellent rate performance with a high capacity of 137 mAh g-1 at 5.0 A g-1 .

Seven-photon absorption from Na+/Bi3+-alloyed Cs2AgInCl6 perovskites.

Nonlinear multi-phonon (2-7) absorption in the Na+/Bi3+-alloyed Cs2AgInCl6 lead-free double perovskites with ∼100% photoluminescence quantum yield and superior stability is observed for the first time, which can be pumped by a femtosecond laser in a wide spectral range (800-2600 nm). First-principles calculations verify that the parity-forbidden transition from the valence band maximum and conduction band minimum (at the Γ point) is not broken by Na+/Bi3+ doping, and strong optical band-to-band absorption occurs at the L&X points. Time-resolved emission spectra evidence that single-photon and multi-photon pumping leads to the same self-trapped exciton transition and high-order nonlinear absorption will not induce a remarkable thermal effect. Finally, we demonstrate that the Cs2Na0.4Ag0.6In0.99Bi0.01Cl6 DP shows great potential for next-generation wavelength-selective and highly sensitive multiphoton imaging applications.

Poly(9,9'-diheylfluorene carbazole) functionalized with reduced graphene oxide: convenient synthesis using nitrogen-based nucleophiles and potential applications in optical limiting.

Covalently functionalized reduced graphene oxide (RGO) sheet was prepared by treating nitrogen-centered anions generated from poly(9,9'-diheylfluorene carbazole) (PCF) with GO. The resultant hybrids with different chemical behavior were separated by centrifugation. The covalent modification was fully characterized by IR spectroscopy, UV/Vis spectroscopy, thermogravimetric analysis (TGA), Raman spectroscopy, TEM, and SEM. It was found that RGO-PCF-s, the soluble part, was split into small platelets with a size of about 200 nm, and the hydrophobic polymer PCF became hydrophilic after wrapping by RGO. The content of RGO in RGO-PCF-s was about 11.9%, and the hybrid material showed good dispersion stability in water. Besides, RGO-PCF-i, the insoluble part, with larger size, displayed excellent optical-limiting response, in which both nonlinear absorption and nonlinear scattering play important roles. As nitrogen-centered anions are an important type of intermediates in chemistry, this one-step "grafting-to" strategy could be used to obtain RGO-based materials with different applications.

Carbon-coated MoS1.5Te0.5 nanocables for efficient sodium-ion storage in non-aqueous dual-ion batteries.

Sodium-based dual-ion batteries have received increased attention owing to their appealing cell voltage (i.e., >3 V) and cost-effective features. However, the development of high-performance anode materials is one of the key elements for exploiting this electrochemical energy storage system at practical levels. Here, we report a source-template synthetic strategy for fabricating a variety of nanowire-in-nanotube MSxTey@C (M = Mo, W, Re) structures with an in situ-grown carbon film coating, termed as nanocables. Among the various materials prepared, the MoS1.5Te0.5@C nanocables are investigated as negative electrode active material in combination with expanded graphite at the positive electrode and NaPF6-based non-aqueous electrolyte solutions for dual-ion storage in coin cell configuration. As a result, the dual-ion lab-scale cells demonstrate a prolonged cycling lifespan with 97% capacity retention over 1500 cycles and a reversible capacity of about 101 mAh g-1 at specific capacities (based on the mass of the anode) of 1.0 A g-1 and 5.0 A g-1, respectively.

Pseudocapacitive Vanadium Nitride Quantum Dots Modified One-Dimensional Carbon Cages Enable Highly Kinetics-Compatible Sodium Ion Capacitors.

The kinetics incompatibility between battery-type anode and capacitive-type cathode for sodium ion hybrid capacitors (SIHCs) seriously hinders their overall performance output. Herein, we construct a SIHCs device by coupling with quantum grade vanadium nitride (VN) nanodots anchored in one-dimensional N/F co-doped carbon nanofiber cages hybrids (VNQDs@PCNFs-N/F) as the freestanding anode and the corresponding activated N/F co-doped carbon nanofiber cages (APCNFs-N/F) as cathode. The strong coupling of VN quantum dots with N/F co-doped 1D conductive carbon cages effectively facilitates the ion/electron transport and intercalation-conversion-deintercalation reactions, ensuring fast sodium storage to surmount aforesaid kinetics incompatibility. Additionally, density functional theory calculations cogently manifest that the abundant active sites in the VNQDs@PCNFs-N/F configuration boost the Na+ adsorption/reaction activity well which will promote both "intrinsic" and "extrinsic" pseudocapacitance and further improve anode kinetics. Consequently, the assembled SIHCs device can achieve high energy densities of 157.1 and 95.0 Wh kg-1 at power densities of 198.8 and 9100.5 W kg-1, respectively, with an ultralong cycling life over 8000 cycles. This work further verified the feasibility of kinetics-compatible electrode design strategy toward metal ion hybrid capacitors.

Synthesis of a Low-Cost Thiophene-Indoloquinoxaline Polymer Donor and Its Application to Polymer Solar Cells.

A simple wide-bandgap conjugated polymer based on indoloquinoxaline unit (PIQ) has been newly designed and synthesized via cheap and commercially available starting materials. The basic physicochemical properties of the PIQ have been investigated. PIQ possesses a broad and strong absorption band in the wavelength range of 400~660 nm with a bandgap of 1.80 eV and lower-lying highest occupied molecular orbital energy level of -5.58 eV. Polymer solar cells based on PIQ and popular acceptor Y6 blend display a preliminarily optimized power conversion efficiency of 6.4%. The results demonstrate indoloquinoxaline is a promising building unit for designing polymer donor materials for polymer solar cells.