Real-Time TEM Observation of the Role of Defects on Nickel Silicide Propagation in Silicon Nanowires.

Metal silicides have received significant attention due to their high process compatibility, low resistivity, and structural stability. In nanowire (NW) form, they have been widely prepared using metal diffusion into preformed Si NWs, enabling compositionally controlled high-quality metal silicide nanostructures. However, unlocking the full potential of metal silicide NWs for next-generation nanodevices requires an increased level of mechanistic understanding of this diffusion-driven transformation. Herein, using in situ transmission electron microscopy (TEM), we investigated the defect-controlled silicide formation dynamics in one-dimensional NWs. A solution-based synthetic route was developed to form Si NWs anchored to Ni NW stems as an optimal platform for in situ TEM studies of metal silicide formation. Multiple in situ annealing experiments led to Ni diffusion from the Ni NW stem into the Si NW, forming a nickel silicide. We observed the dynamics of Ni propagation in straight and kinked Si NWs, with some regions of the NWs acting as Ni sinks. In NWs with high defect distribution, we obtained direct evidence of nonuniform Ni diffusion and silicide retardation. The findings of this study provide insights into metal diffusion and silicide formation in complex NW structures, which are crucial from fundamental and application perspectives.

Solution processable Si/Ge heterostructure NWs enabling anode mass reduction for practical full-cell Li-ion batteries.

Here, we report the solution phase synthesis of axial heterostructure Si and Ge (hSG) nanowires (NWs). The NWs were grown in a high boiling point solvent from a low-cost Sn powder to achieve a powder form product which represents an attractive route from lab-scale to commercial application. Slurry processed anodes of the NWs were investigated in half-cell (versus Li-foil) and full-cell (versus NMC811) configurations of a lithium ion battery (LIB). The hSG NW anodes yielded capacities of 1040 mA h g-1 after 150 cycles which corresponds to a 2.8 times increase compared to a standard graphite (372 mA h g-1) anode. Given the impressive specific and areal capacities of the hSG anodes, a full-cell test against a high areal capacity NMC811 cathode was examined. In full-cell configuration, use of the hSG anode resulted in a massive anode mass reduction of 50.7% compared to a standard graphite anode. The structural evolution of the hSG NW anodes into an alloyed SiGe porous mesh network was also investigated using STEM, EDX and Raman spectroscopy as a function of cycle number to fully elucidate the lithiation/delithiation mechanism of the promising anode material.

Colloidal Synthesis of Multinary Alkali-Metal Chalcogenides Containing Bi and Sb: An Emerging Class of I-V-VI2 Nanocrystals with Tunable Composition and Interesting Properties.

The growth mechanism and synthetic controls for colloidal multinary metal chalcogenide nanocrystals (NCs) involving alkali metals and the pnictogen metals Sb and Bi are unknown. Sb and Bi are prone to form metallic nanocrystals that stay as impurities in the final product. Herein, we synthesize colloidal NaBi1-xSbxSe2-ySy NCs using amine-thiol-Se chemistry. We find that ternary NaBiSe2 NCs initiate with Bi0 nuclei and an amorphous intermediate nanoparticle formation that gradually transforms into NaBiSe2 upon Se addition. Furthermore, we extend our methods to substitute Sb in place of Bi and S in place of Se. Our findings show the initial quasi-cubic morphology transforms into a spherical shape upon increased Sb substitution, and the S incorporation promotes elongation along the <111> direction. We further investigate the thermoelectric transport properties of the Sb-substituted material displaying very low thermal conductivity and n-type transport behavior. Notably, the NaBi0.75Sb0.25Se2 material exhibits an ultralow thermal conductivity of 0.25 W·m-1·K-1 at 596 K with an average thermal conductivity of 0.35 W·m-1·K-1 between 358 and 596 K and a ZTmax of 0.24.

Cu Current Collector with Binder-Free Lithiophilic Nanowire Coating for High Energy Density Lithium Metal Batteries.

Despite significant efforts to fabricate high energy density (ED) lithium (Li) metal anodes, problems such as dendrite formation and the need for excess Li (leading to low N/P ratios) have hampered Li metal battery (LMB) development. Here, the use of germanium (Ge) nanowires (NWs) directly grown on copper (Cu) substrates (Cu-Ge) to induce lithiophilicity and subsequently guide Li ions for uniform Li metal deposition/stripping during electrochemical cycling is reported. The NW morphology along with the formation of the Li15 Ge4 phase promotes uniform Li-ion flux and fast charge kinetic, resulting in the Cu-Ge substrate demonstrating low nucleation overpotentials of 10 mV (four times lower than planar Cu) and high Columbic efficiency (CE) efficiency during Li plating/stripping. Within a full-cell configuration, the Cu-Ge@Li - NMC cell delivered a 63.6% weight reduction at the anode level compared to a standard graphite-based anode, with impressive capacity retention and average CE of over 86.5% and 99.2% respectively. The Cu-Ge anodes are also paired with high specific capacity sulfur (S) cathodes, further demonstrating the benefits of developing surface-modified lithiophilic Cu current collectors, which can easily be integrated at the industrial scale.

Precursor-Mediated Colloidal Synthesis of Compositionally Tunable Cu-Sb-M-S (M = Zn, Co, and Ni) Nanocrystals and Their Transport Properties.

The solution-based colloidal synthesis of multinary semiconductor compositions has allowed the design of new inorganic materials impacting a large variety of applications. Yet there are certain compositions that have remained elusive-particularly quaternary structures of transition metal-based (e.g., Co, Zn, Ni, Fe, Mn, and Cr) copper antimony chalcogenides. These are widely sought for tuning the electrical and thermal conductivity as a function of the size, composition, and crystal phase. In this work, a facile hot injection approach for the synthesis of three different tetrahedrite-substituted nanocrystals (NCs) (Cu10Zn2Sb4S13, Cu10Co2Sb4S13, and Cu10Ni1.5Sb4S13) and their growth mechanisms are investigated. We reveal that the interplay between the Zn, Ni, and Co precursors on the basis of thiophilicity is key to obtaining pure phase NCs with controlled size and shape. While all of the synthesized crystal phases display outstanding low thermal conductivity, the Cu10.5Sb4Ni1.5S13 system shows the most enhanced electrical conductivity compared to Cu10Zn2Sb4S13 and Cu10Co2Sb4S13. This study highlights an effective synthesis strategy for the growth of complex quaternary nanocrystals and their high potential for application in thermoelectrics.

Subsuming the Metal Seed to Transform Binary Metal Chalcogenide Nanocrystals into Multinary Compositions.

Direct colloidal synthesis of multinary metal chalcogenide nanocrystals typically develops dynamically from the binary metal chalcogenide nanocrystals with the subsequent incorporation of additional metal cations from solution during the growth process. Metal seeding of binary and multinary chalcogenides is also established, although the seed is solely a catalyst for nanocrystal nucleation and the metal from the seed has never been exploited as active alloying nuclei. Here we form colloidal Cu-Bi-Zn-S nanorods (NRs) from Bi-seeded Cu2-xS heterostructures. The evolution of these homogeneously alloyed NRs is driven by the dissolution of the Bi-rich seed and recrystallization of the Cu-rich stem into a transitional segment, followed by the incorporation of Zn2+ to form the quaternary Cu-Bi-Zn-S composition. The present study also reveals that the variation of Zn concentration in the NRs modulates the aspect ratio and affects the nature of the majority charge carriers. The NRs exhibit promising thermoelectric properties with very low thermal conductivity values of 0.45 and 0.65 W/mK at 775 and 605 K, respectively, for Zn-poor and Zn-rich NRs. This study highlights the potential of metal seed alloying as a direct growth route to achieving homogeneously alloyed NRs compositions that are not possible by conventional direct methods or by postsynthetic transformations.

Phosphine free synthesis of copper telluride nanocrystals in 1D and 2D shapes using Dipehylditelluride (DPDTe) as an air-stable source.

In this paper, we have developed a 'phosphine-free' method for synthesising copper telluride nanocrystals using diphenyl ditelluride as an air-stable tellurium source. The diphenyl ditelluride is shown to have optimal reactivity for the colloidal synthesis of Cu2Te, allowing optimal control over the phase and morphology. Using this unexplored Te precursor for copper telluride synthesis, 1D nanorods of hexagonal phase (Cu2Te) were synthesised at a moderate temperature of 180 °C. The precise control over key parameters for this system results in Cu2-xTe nanocrystals forming with varied shapes (1D nanorods and 2D nanoplates), sizes, and crystal phases (hexagonal Cu2Te and orthorhombic Cu1.43Te).

Temperature induced diameter variation of silicon nanowires via a liquid-solid phase transition in the Zn seed.

Herein, we demonstrate the ability of Zn to catalyze the growth of Si nanowires via reaction temperature determined, vapour-liquid-solid (VLS) or vapour-solid-solid (VSS) growth mechanisms. This is the first reported use of a type B catalyst to grow Si nanowires via the VSS mechanism to our knowledge whereby the highly faceted Zn seeds resulted in an increased NW diameter. This was used to induce diameter variations along the axial length of individual nanowires by transitioning between VLS and VSS growth.

Direct Growth of Si, Ge, and Si-Ge Heterostructure Nanowires Using Electroplated Zn: An Inexpensive Seeding Technique for Li-Ion Alloying Anodes.

A scalable and cost-effective process is used to electroplate metallic Zn seeds on stainless steel substrates. Si and Ge nanowires (NWs) are subsequently grown by placing the electroplated substrates in the solution phase of a refluxing organic solvent at temperatures >430 °C and injecting the respective liquid precursors. The native oxide layer formed on reactive metals such as Zn can obstruct NW growth and is removed in situ by injecting the reducing agent LiBH4 . The findings show that the use of Zn as a catalyst produces defect-rich Si NWs that can be extended to the synthesis of Si-Ge axial heterostructure NWs with an atomically abrupt Si-Ge interface. As an anode material, the as grown Zn seeded Si NWs yield an initial discharge capacity of 1772 mAh g-1 and a high capacity retention of 85% after 100 cycles with the active participation of both Si and Zn during cycling. Notably, the Zn seeds actively participate in the Li-cycling activities by incorporating into the Si NWs body via a Li-assisted welding process, resulting in restructuring the NWs into a highly porous network structure that maintains a stable cycling performance.