Plasmon‐Enhanced Spectroscopies with Shell‐Isolated Nanoparticles

Shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS), due to its versatility, has been able to break the long‐term limitations of the material‐ and substrate‐specific generalities in the traditional field of surface‐enhanced Raman spectroscopy. With a shell‐isolated work principle, this method provides an opportunity to investigate successfully in surface, biological systems, energetic materials, and environmental sciences. Both the shell material and core morphology are being improved continuously to meet the requirements in diverse systems, such as the electrochemical studies at single crystal electrode surfaces, in situ monitoring of photoinduced reaction processes, practical applications in energy conversion and storage, inspections in food safety, and the surface‐enhanced fluorescence. Predictably, the concept of shell‐isolated nanoparticle‐enhancement could be expanded to the wider range for the performance of plasmon‐enhanced spectral modifications.     

In Situ Observation of Crystallization of Methylammonium Lead Iodide Perovskite from Microdroplets

It is of great importance to investigate the crystallization of organometallic perovskite from solution for enhancing performance of perovskite solar cells. Here, this study develops a facile method for in situ observation of crystallization and growth of the methylammonium lead iodide (MAPbI₃) perovskite from microdroplets ejected by an alternating viscous and inertial force jetting method. It is found that there are two crystallization modes when MAPbI₃ grows from the CH₃NH₃I (MAI)/PbI₂/N,N‐dimethylformamide (DMF) solution: needle precursors and granular perovskites. Generally, needle Lewis adduct of MAPbI₃·DMF tends to nucleate and grow from the solution due to low solubility of PbI₂. The growth of MAPbI₃·DMF depends on both the concentration of MAI and temperature. It tends to form large perovskite domains on substrates at high temperature. The MAPbI₃·DMF coverts to nanocrystalline perovskite due to lattice shrinkage when DMF molecules escape from the Lewis adduct. Granular perovskite can also directly nucleate from the solution at high concentration of MAI due to compositional segregation.     

Surface Energy and Surface Stability of Ag Nanocrystals at Elevated Temperatures and Their Dominance in Sublimation‐Induced Shape Evolution

The surface energy and surface stability of Ag nanocrystals (NCs) are under debate because the measurable values of the surface energy are very inconsistent, and the indices of the observed thermally stable surfaces are apparently in conflict. To clarify this issue, a transmission electron microscope is used to investigate these problems in situ with elaborately designed carbon‐shell‐capsulated Ag NCs. It is demonstrated that the {111} surfaces are still thermally stable at elevated temperatures, and the victory of the formation of {110} surfaces over {111} surfaces on the Ag NCs during sublimation is due to the special crystal geometry. It is found that the Ag NCs behave as quasiliquids during sublimation, and the cubic NCs represent a featured shape evolution, which is codetermined by both the wetting equilibrium at the Ag–C interface and the relaxation of the system surface energy. Small Ag NCs (≈10 nm) no longer maintain the wetting equilibrium observed in larger Ag NCs, and the crystal orientations of ultrafine Ag NCs (≈6 nm) can rotate to achieve further shape relaxation. Using sublimation kinetics, the mean surface energy of Ag NCs at 1073 K is calculated to be 1.1–1.3 J m^?2.     

Efficient and 1,8-diiodooctane-free ternary organic solar cells fabricated via nanoscale morphology tuning using small-molecule dye additive

The ternary strategy for incorporating multiple photon-sensitive components into a single junction has emerged as an effective method for optimizing the nanoscale morphology and improving the device performance of organic solar cells (OSCs).In this study,efficient and stable ternary OSCs were achieved by introducing the small-molecule dye (5E,5'E)-5,5'-(4',4″-(1,2-diphenylethene-1,2-diyl)bis(biphenyl-4',4-diyl))bis(methan-1-yl-1-ylidene)bis(3-ethyl-2-thioxothia zolidin-4-one) (BTPERn) into poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiopheneco-3-fluorothieno[3,4-b]thiophene-2-carboxylate] (PTB7-Th):[6,6]-phenyl C71 butyric acid methyl ester (PC71BM) blend films processed using a 1,8-diiodooctane (DIO)-free solvent.The incorporation of BTPE-Rn enhanced the short-circuit current density and fill factor of the ternary OSCs compared with those of binary OSCs.An investigation of the optical,electronic,and morphological properties of the ternary blends indicated that the third component of BTPE-Rn not only promoted the photon utilization of blends through the energy-transfer process but also improved the electron mobility of the blends owing to the fullerene-rich nanophase optimization.More importantly,this ternary strategy of utilizing a small-molecule dye to replace the photounstable DIO additive enhanced the operational stability of the OSCs.     

Epitaxial growth of large-area and highly crystalline anisotropic ReSe<Subscript>2</Subscript> atomic layer

The anisotropic two-dimensional (2D) layered material rhenium disulfide (ReSe2) has attracted considerable attention because of its unusual properties and promising applications in electronic and optoelectronic devices.However,because of its low lattice symmetry and interlayer decoupling,anisotropic growth and out-of-plane growth occur easily,yielding thick flakes,dendritic structure,or flower-like structure.In this study,we demonstrated a bottom-up method for the controlled and scalable synthesis of ReSe2 by van der Waals epitaxy.To achieve controllable growth,a micro-reactor with a confined reaction space was constructed by stacking two mica substrates in the chemical vapor deposition system.Within the confined reaction space,the nucleation density and growth rate of ReSe2 were significantly reduced,favoring the large-area synthesis of ReSe2 with a uniform monolayer thickness.The morphological evolution of ReSe2 with growth temperature indicated that the anisotropic growth was suppressed at a low growth temperature (＜600 ℃).Field-effect transistors employing the grown ReSe2 exhibited p-type conduction with a current ON/OFF ratio up to 10s and a hole carrier mobility of 0.98 cm2/(V.s).Furthermore,the ReSe2 device exhibited an outstanding photoresponse to near-infrared light,with responsivity up to 8.4 and 5.1 A/W for 850-and 940-nm light,respectively.This work not only promotes the large-scale application of ReSe2 in high-performance electronic devices but also clarifies the growth mechanism of low-lattice symmetry 2D materials.     

Walnut-inspired microsized porous silicon/graphene core–shell composites for high-performance lithium-ion battery anodes

Silicon is considered an exceptionally promising alternative to the most commonly used material, graphite, as an anode for next-generation lithium-ion batteries, as it has high energy density owing to its high theoretical capacity and abundant storage. Here, microsized walnut-like porous silicon/reduced graphene oxide (P-Si/rGO) core–shell composites are successfully prepared via in situ reduction followed by a dealloying process. The composites show specific capacities of more than 2,100 mAh·g^?1 at a current density of 1,000 mA·g^?1, 1,600 mAh·g^?1 at 2,000 mA·g^?1, 1,500 mAh·g^?1 at 3,000 mA·g^?1, 1,200 mAh·g^?1 at 4,000 mA·g^?1, and 950 mAh·g^?1 at 5,000 mA·g^?1, and maintain a value of 1,258 mAh·g^?1 after 300 cycles at a current density of 1,000 mA·g^?1. Their excellent rate performance and cycling stability can be attributed to the unique structural design: 1) The graphene shell dramatically improves the conductivity and stabilizes the solid–electrolyte interface layers; 2) the inner porous structure supplies sufficient space for silicon expansion; 3) the nanostructure of silicon can prevent the pulverization resulting from volume expansion stress. Notably, this in situ reduction method can be applied as a universal formula to coat graphene on almost all types of metals and alloys of various sizes, shapes, and compositions without adding any reagents to afford energy storage materials, graphene-based catalytic materials, graphene-enhanced composites, etc.

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