Hexagonal Hybrid Bismuthene by Molecular Interface Engineering.

High-quality devices based on layered heterostructures are typically built from materials obtained by complex solid-state physical approaches or laborious mechanical exfoliation and transfer. Meanwhile, wet-chemically synthesized materials commonly suffer from surface residuals and intrinsic defects. Here, we synthesize using an unprecedented colloidal photocatalyzed, one-pot redox reaction a few-layers bismuth hybrid of "electronic grade" structural quality. Intriguingly, the material presents a sulfur-alkyl-functionalized reconstructed surface that prevents it from oxidation and leads to a tuned electronic structure that results from the altered arrangement of the surface. The metallic behavior of the hybrid is supported by ab initio predictions and room temperature transport measurements of individual nanoflakes. Our findings indicate how surface reconstructions in two-dimensional (2D) systems can promote unexpected properties that can pave the way to new functionalities and devices. Moreover, this scalable synthetic process opens new avenues for applications in plasmonics or electronic (and spintronic) device fabrication. Beyond electronics, this 2D hybrid material may be of interest in organic catalysis, biomedicine, or energy storage and conversion.

Metal-Metal Bonding as an Electrode Design Principle in the Low-Strain Cluster Compound LiScMo3O8.

Electrode materials for Li+-ion batteries require optimization along several disparate axes related to cost, performance, and sustainability. One of the important performance axes is the ability to retain structural integrity though cycles of charge/discharge. Metal-metal bonding is a distinct feature of some refractory metal oxides that has been largely underutilized in electrochemical energy storage, but that could potentially impact structural integrity. Here LiScMo3O8, a compound containing triangular clusters of metal-metal bonded Mo atoms, is studied as a potential anode material in Li+-ion batteries. Electrons inserted though lithiation are localized across rigid Mo3 triangles (rather than on individual metal ions), resulting in minimal structural change as suggested by operando diffraction. The unusual chemical bonding allows this compound to be cycled with Mo atoms below a formally +4 valence state, resulting in an acceptable voltage regime that is appropriate for an anode material. Several characterization methods including potentiometric entropy measurements indicate two-phase regions, which are attributed through extensive first-principles modeling to Li+ ordering. This study of LiScMo3O8 provides valuable insights for design principles for structural motifs that stably and reversibly permit Li+ (de)insertion.

Formation and thermal stability of two-phase microstructures in Al-containing refractory compositionally complex alloys.

Phase separation into an A2+B2 two-phase microstructure in refractory compositionally complex alloys (RCCA) has been speculated as being spinodal in nature with continuous chemical distribution during the separation. However, these reactions might instead occur as precipitation by nucleation and growth. In order to unequivocally elucidate the distinct nature of phase separation sequence in RCCA from the system Ta-Mo-Ti-Cr-Al, atom probe tomography and electron microscopy techniques were utilized on samples that were annealed over multiple orders of magnitude in time. The composition 82(TaMoTi)-8Cr-10Al (at.%) was chosen, as it exhibits a two-phase microstructure, with a desired A2 matrix and embedded B2 phase. Quenching the samples from 1200°C resulted in a microstructure consisting of ordered clusters (2 nm) of distinct chemical composition. Subsequent annealing at 800°C to 1000°C leads to an increase in the volume fraction of the precipitating phase, which saturates after 10 h. Further annealing leads to the ripening of the microstructure; however, the absolute size of the precipitates stays <100 nm even after 1000 h. For the investigated conditions, the interface between matrix and precipitate can be considered sharp within the resolution of the applied techniques and no significant change in the transition of chemical composition across the interface is observed. Therefore, the phase separation mechanism is confirmed to be phase nucleation and growth in contrast to the possible spinodal decomposition, as hypothesized for other RCCA systems. The impact of precipitation and coarsening on the hardness of the alloy is discussed.

Enhanced Performance of Laser-Induced Graphene Supercapacitors via Integration with Candle-Soot Nanoparticles.

Laser-induced graphene (LIG) has been emerging as a promising electrode material for supercapacitors due to its cost-effective and straightforward fabrication approach. However, LIG-based supercapacitors still face challenges with limited capacitance and stability. To overcome these limitations, in this work, we present a novel, cost-effective, and facile fabrication approach by integrating LIG materials with candle-soot nanoparticles. The composite electrode is fabricated by laser irradiation on a Kapton sheet to generate LIG material, followed by spray-coating with candle-soot nanoparticles and annealing. Materials characterization reveals that the annealing process enables a robust connection between the nanoparticles and the LIG materials and enhances nanoparticle graphitization. The prepared supercapacitor yields a maximum specific capacitance of 15.1 mF/cm2 at 0.1 mA/cm2, with a maximum energy density of 2.1 µWh/cm2 and a power density of 50 µW/cm2. Notably, the synergistic activity of candle soot and LIG surpasses the performances of previously reported LIG-based supercapacitors. Furthermore, the cyclic stability of the device demonstrates excellent capacitance retention of 80% and Coulombic efficiency of 100% over 10000 cycles.

Dramatic Impact of Materials Combinations on the Chemical Organization of Core-Shell Nanocrystals: Boosting the Tm3+ Emission above 1600 nm.

This article represents the first foray into investigating the consequences of various material combinations on the short-wave infrared (SWIR, 1000-2000 nm) performance of Tm-based core-shell nanocrystals (NCs) above 1600 nm. In total, six different material combinations involving two different types of SWIR-emitting core NCs (α-NaTmF4 and LiTmF4) combined with three different protecting shell materials (α-NaYF4, CaF2, and LiYF4) have been synthesized. All corresponding homo- and heterostructured NCs have been meticulously characterized by powder X-ray diffraction and electron microscopy techniques. The latter revealed that out of the six investigated combinations, only one led to the formation of a true core-shell structure with well-segregated core and shell domains. The direct correlation between the downshifting performance and the spatial localization of Tm3+ ions within the final homo- and heterostructured NCs is established. Interestingly, to achieve the best SWIR performance, the formation of an abrupt interface is not a prerequisite, while the existence of a pure (even thin) protective shell is vital. Remarkably, although all homo- and heterostructured NCs have been synthesized under the exact same experimental conditions, Tm3+ SWIR emission is either fully quenched or highly efficient depending on the type of material combination. The most efficient combination (LiTmF4/LiYF4) achieved a high photoluminescence quantum yield of 39% for SWIR emission above 1600 nm (excitation power density in the range 0.5-3 W/cm2) despite significant intermixing. From now on, highly efficient SWIR-emitting probes with an emission above 1600 nm are within reach to unlock the full potential of in vivo SWIR imaging.

Microarchitected Compliant Scaffolds of Pyrolytic Carbon for 3D Muscle Cell Growth.

The integration of additive manufacturing technologies with the pyrolysis of polymeric precursors enables the design-controlled fabrication of architected 3D pyrolytic carbon (PyC) structures with complex architectural details. Despite great promise, their use in cellular interaction remains unexplored. This study pioneers the utilization of microarchitected 3D PyC structures as biocompatible scaffolds for the colonization of muscle cells in a 3D environment. PyC scaffolds are fabricated using micro-stereolithography, followed by pyrolysis. Furthermore, an innovative design strategy using revolute joints is employed to obtain novel, compliant structures of architected PyC. The pyrolysis process results in a pyrolysis temperature- and design-geometry-dependent shrinkage of up to 73%, enabling the geometrical features of microarchitected compatible with skeletal muscle cells. The stiffness of architected PyC varies with the pyrolysis temperature, with the highest value of 29.57 ± 0.78 GPa for 900 °C. The PyC scaffolds exhibit excellent biocompatibility and yield 3D cell colonization while culturing skeletal muscle C2C12 cells. They further induce good actin fiber alignment along the compliant PyC construction. However, no conclusive myogenic differentiation is observed here. Nevertheless, these results are highly promising for architected PyC scaffolds as multifunctional tissue implants and encourage more investigations in employing compliant architected PyC structures for high-performance tissue engineering applications.

Photonic Curing Enables Ultrarapid Processing of Highly Conducting ß-Cu2-δSe Printed Thermoelectric Films in Less Than 10 ms.

It has been a challenge to obtain high electrical conductivity in inorganic printed thermoelectric (TE) films due to their high interfacial resistance. In this work, we report a facile synthesis process of Cu-Se-based printable ink for screen printing. A highly conducting TE ß-Cu2-δSe phase forms in the screen-printed Cu-Se-based film through ≤10 ms sintering using photonic-curing technology, minimizing the interfacial resistance. This enables overcoming the major challenges associated with printed thermoelectrics: (a) to obtain the desired phase, (b) to attain high electrical conductivity, and (c) to obtain flexibility. Furthermore, the photonic-curing process reduces the synthesis time of the TE ß-Cu2-δSe film from several days to a few milliseconds. The sintered film exhibits a remarkably high electrical conductivity of ∼3710 S cm-1 with a TE power factor of ∼100 µW m-1 K-2. The fast processing and high conductivity of the film could also be potentially useful for different printed electronics applications.

High Figure-of-Merit Telluride-Based Flexible Thermoelectric Films through Interfacial Modification via Millisecond Photonic-Curing for Fully Printed Thermoelectric Generators.

The thermoelectric generator (TEG) shows great promise for energy harvesting and waste heat recovery applications. Cost barriers for this technology could be overcome by using printing technologies. However, the development of thermoelectric (TE) materials that combine printability, high-efficiency, and mechanical flexibility is a serious challenge. Here, flexible (SbBi)2 (TeSe)3 -based screen-printed TE films exhibiting record-high figure of merits (ZT) and power factors are reported. A high power factor of 24 µW cm-1  K-2 (ZTmax  ≈ 1.45) for a p-type film and a power factor of 10.5 µW cm-1  K-2 (ZTmax  ≈ 0.75) for an n-type film are achieved. The TE inks, comprised of p-Bi0.5 Sb1.5 Te3 (BST)/n-Bi2 Te2.7 Se0.3 (BT) and a Cu-Se-based inorganic binder (IB), are prepared by a one-pot synthesis process. The TE inks are printed on different substrates and sintered using photonic-curing leading to the formation of a highly conducting ß-Cu2- δ Se phase that connects "microsolders," the grains resulting in high-performance. Folded TEGs (f-TEGs) are fabricated using the materials. A half-millimeter thick f-TEG exhibits an open-circuit voltage (VOC ) of 203 mV with a maximum power density (pmax ) of 5.1 W m-2 at ∆T = 68 K. This result signifies that a few millimeters thick f-TEG could power Internet-of-Things (IoTs) devices converting low-grade heat to electricity.

Electrospun carbon nanofibre-assisted patterning of metal oxide nanostructures.

This work establishes carbon nanofibre-mediated patterning of metal oxide nanostructures, through the combination of electrospinning and vapor-phase transport growth. Electrospinning of a suitable precursor with subsequent carbonization results in the patterning of catalyst gold nanoparticles embedded within carbon nanofibres. During vapor-phase transport growth, these nanofibres allow preferential growth of one-dimensional metal oxide nanostructures, which grow radially outward from the nanofibril axis, yielding a hairy caterpillar-like morphology. The synthesis of metal oxide caterpillars is demonstrated using zinc oxide, indium oxide, and tin oxide. Source and substrate temperatures play the most crucial role in determining the morphology of the metal oxide caterpillars, whereas the distribution of the nanofibres also has a significant impact on the overall morphology. Introducing the current methodology with near-field electrospinning further facilitates user-defined custom patterning of metal oxide caterpillar-like structures.

Realizing High Thermoelectric Performance of Bi-Sb-Te-Based Printed Films through Grain Interface Modification by an In Situ-Grown ß-Cu2-δSe Phase.

It has been a substantial challenge to develop a printed thermoelectric (TE) material with a figure-of-merit ZT > 1. In this work, high ZT p-type Bi0.5Sb1.5Te3-based printable TE materials have been advanced by interface modification of the TE grains with a nonstoichiometric ß-Cu2-δSe-based inorganic binder (IB) through a facile printing-sintering process. As a result, a very high TE power factor of ∼17.5 µW cm-1 K-2 for a p-type printed material is attained in the optimized compounds at room temperature (RT). In addition, a high ZT of ∼1.2 at RT and of ∼1.55 at 360 K is realized using thermal conductivity (κ) of a pellet made of the prepared printable material containing 10 wt % of IB. Using the same material for p-type TE legs and silver paste for n-type TE legs, a printed TE generator (print-TEG) of four thermocouples has been fabricated for demonstration. An open-circuit voltage (VOC) of 14 mV and a maximum power output (Pmax) of 1.7 µW are achieved for ΔT = 40 K for the print-TEG.