Salt-Assisted Vapor-Liquid-Solid Growth of 1D van der Waals Materials.

The method of salt-assisted vapor-liquid-solid (VLS) growth is introduced to synthesize 1D nanostructures of trichalcogenide van der Waals (vdW) materials, exemplified by niobium trisulfide (NbS). The method uses a unique catalyst consisting of an alloy of Au and an alkali metal halide (NaCl) to enable rapid and directional growth. High yields of two types of NbS 1D nanostructures, nanowires and nanoribbons, each with sub-ten nanometer diameter, tens of micrometers length, and distinct 1D morphology and growth orientation are demonstrated.

Programming Semiconductor Nanowire Composition with Sub-100 nm Resolution via the Geode Process.

We demonstrate the vapor-liquid-solid growth of single-crystalline i-Si, i-Si/n-Si, and SiGe/SiGe nanowires via the Geode process. By enabling nanowire growth on the large internal surface area of a microcapsule powder, the Geode process improves the scalability of semiconductor nanowire manufacturing while maintaining nanoscale programmability. Here, we show that heat and mass transport limitations introduced by the microcapsule wall are negligible, enabling the same degree of compositional control for nanowires grown inside microcapsules and on conventional flat substrates.

Impact of Porosity and Boundary Scattering on Thermal Transport in Diameter-Modulated Nanowires.

We study the thermal conductivity of diameter-modulated Si nanowires to understand the impact of different nanoscale transport mechanisms as a function of nanowire morphology. Our investigation couples transient suspended microbridge measurements of diameter-modulated Si nanowires synthesized via vapor-liquid-solid growth and dopant-selective etching with predictive Boltzmann transport modeling. We show that the presence of a low thermal conductivity phase (i.

Bottom-up nanoscale patterning and selective deposition on silicon nanowires.

We demonstrate a bottom-up process for programming the deposition of coaxial thin films aligned to the underlying dopant profile of semiconductor nanowires. Our process synergistically combines three distinct methods-vapor-liquid-solid nanowire growth, selective coaxial lithography via etching of surfaces (SCALES), and area-selective atomic layer deposition (AS-ALD)-into a cohesive whole. Here, we study ZrOon Si nanowires as a model system.

One-dimensional twisted and tubular structures of zinc oxide by semiconductor-catalyzed vapor-liquid-solid synthesis.

The exploration of unconventional catalysts for the vapor-liquid-solid synthesis of one-dimensional materials promises to yield new morphologies and functionality. Here, we show, for the model ZnO system, that unusual nanostructures can be produced via a semiconductor (Ge) catalyst. As well as the usual straight nanowires, we describe two other distinct morphologies: twisted nanowires and twisted nanotubes.

Bottom-Up Masking of Si/Ge Surfaces and Nanowire Heterostructures Surface-Initiated Polymerization and Selective Etching.

The fully bottom-up and scalable synthesis of complex micro/nanoscale materials and functional devices requires masking methods to define key features and direct the deposition of various coatings and films. Here, we demonstrate selective coaxial lithography etching of surfaces (SCALES), an enabling bottom-up process to add polymer masks to micro/nanoscale objects. SCALES is a three-step process, including (1) bottom-up synthesis of compositionally modulated structures, (2) surface-initiated polymerization of a conformal mask, and (3) selective removal of the mask only from regions whose underlying surface is susceptible to an etchant.

Self-regenerating giant hyaluronan polymer brushes.

Tailoring interfaces with polymer brushes is a commonly used strategy to create functional materials for numerous applications. Existing methods are limited in brush thickness, the ability to generate high-density brushes of biopolymers, and the potential for regeneration. Here we introduce a scheme to synthesize ultra-thick regenerating hyaluronan polymer brushes using hyaluronan synthase.

Contactless Electrical and Structural Characterization of Semiconductor Nanowires with Axially Modulated Doping Profiles.

Efficient characterization of semiconductor nanowires having complex dopant profiles or heterostructures is critical to fully understand these materials and the devices built from them. Existing electrical characterization techniques are slow and laborious, particularly for multisegment nanowires, and impede the statistical understanding of highly variable samples. Here, it is shown that electro-orientation spectroscopy (EOS)-a high-throughput, noncontact method for statistically characterizing the electrical properties of entire nanowire ensembles-can determine the conductivity and dimensions of two distinct segments in individual Si nanowires with axially encoded dopant profiles.

Sub-diffractional waveguiding by mid-infrared plasmonic resonators in semiconductor nanowires.

Chains of nanoscale plasmonic resonators are capable of sub-diffractional waveguiding and have applications in nanophotonics and thermal radiation transport. Practical uses have largely been limited, however, due to high optical losses or low group velocities. Here, we predict the waveguide performance of a material structure capable of overcoming these limitations: plasmonic resonators embedded in high-dielectric nanowires.

Atomic-Scale Choreography of Vapor-Liquid-Solid Nanowire Growth.

Functional materials and devices require nanoscale control of morphology, crystal structure, and composition. Vapor-liquid-solid (VLS) crystal growth and its related growth modes enable the synthesis of 1D nanostructures, commonly called "nanowires", where the necessary nanoscale heterogeneity can be encoded axially. During the VLS process, a seed particle collects atoms and directs the nucleation of crystalline material.

Process Principles for Large-Scale Nanomanufacturing.

Nanomanufacturing-the fabrication of macroscopic products from well-defined nanoscale building blocks-in a truly scalable and versatile manner is still far from our current reality. Here, we describe the barriers to large-scale nanomanufacturing and identify routes to overcome them. We argue for nanomanufacturing systems consisting of an iterative sequence of synthesis/assembly and separation/sorting unit operations, analogous to those used in chemicals manufacturing.

Surface Hydrogen Enables Subeutectic Vapor-Liquid-Solid Semiconductor Nanowire Growth.

Vapor-liquid-solid nanowire growth below the bulk metal-semiconductor eutectic temperature is known for several systems; however, the fundamental processes that govern this behavior are poorly understood. Here, we show that hydrogen atoms adsorbed on the Ge nanowire sidewall enable AuGe catalyst supercooling and control Au transport. Our approach combines in situ infrared spectroscopy to directly and quantitatively determine hydrogen atom coverage with a "regrowth" step that allows catalyst phase to be determined with ex situ electron microscopy.

High-throughput electrical measurement and microfluidic sorting of semiconductor nanowires.

Existing nanowire electrical characterization tools not only are expensive and require sophisticated facilities, but are far too slow to enable statistical characterization of highly variable samples. They are also generally not compatible with further sorting and processing of nanowires. Here, we demonstrate a high-throughput, solution-based electro-orientation-spectroscopy (EOS) method, which is capable of automated electrical characterization of individual nanowires by direct optical visualization of their alignment behavior under spatially uniform electric fields of different frequencies.

Solid-Liquid-Vapor Etching of Semiconductor Nanowires.

The vapor-liquid-solid (VLS) mechanism enables the bottom-up, or additive, growth of semiconductor nanowires. Here, we demonstrate a reverse process, whereby catalyst atoms are selectively removed from the eutectic catalyst droplet. This process, which is driven by the dicarbonyl precursor 2,3-butanedione, results in axial nanowire etching.

Direct Observation of Transient Surface Species during Ge Nanowire Growth and Their Influence on Growth Stability.

Surface adsorbates are well-established choreographers of material synthesis, but the presence and impact of these short-lived species on semiconductor nanowire growth are largely unknown. Here, we use infrared spectroscopy to directly observe surface adsorbates, hydrogen atoms and methyl groups, chemisorbed to the nanowire sidewall and show they are essential for the stable growth of Ge nanowires via the vapor-liquid-solid mechanism. We quantitatively determine the surface coverage of hydrogen atoms during nanowire growth by comparing ν(Ge-H) absorption bands from operando measurements (i.

Contactless Determination of Electrical Conductivity of One-Dimensional Nanomaterials by Solution-Based Electro-orientation Spectroscopy.

Nanowires of the same composition, and even fabricated within the same batch, often exhibit electrical conductivities that can vary by orders of magnitude. Unfortunately, existing electrical characterization methods are time-consuming, making the statistical survey of highly variable samples essentially impractical. Here, we demonstrate a contactless, solution-based method to efficiently measure the electrical conductivity of 1D nanomaterials based on their transient alignment behavior in ac electric fields of different frequencies.

Optically abrupt localized surface plasmon resonances in si nanowires by mitigation of carrier density gradients.

Spatial control of carrier density is critical for engineering and exploring the interactions of localized surface plasmon resonances (LSPRs) in nanoscale semiconductors. Here, we couple in situ infrared spectral response measurements and discrete dipole approximation (DDA) calculations to show the impact of axially graded carrier density profiles on the optical properties of mid-infrared LSPRs supported by Si nanowires synthesized by the vapor-liquid-solid technique. The region immediately adjacent to each intentionally encoded resonator (i.

Interplay between defect propagation and surface hydrogen in silicon nanowire kinking superstructures.

Semiconductor nanowire kinking superstructures, particularly those with long-range structural coherence, remain difficult to fabricate. Here, we combine high-resolution electron microscopy with operando infrared spectroscopy to show why this is the case for Si nanowires and, in doing so, reveal the interplay between defect propagation and surface chemistry during ⟨211⟩ → ⟨111⟩ and ⟨211⟩ → ⟨211⟩ kinking. Our experiments show that adsorbed hydrogen atoms are responsible for selecting ⟨211⟩-oriented growth and indicate that a twin boundary imparts structural coherence.

Sidewall morphology-dependent formation of multiple twins in Si nanowires.

Precise placement of twin boundaries and stacking faults promises new opportunities to fundamentally manipulate the optical, electrical, and thermal properties of semiconductor nanowires. Here we report on the appearance of consecutive twin boundaries in Si nanowires and show that sidewall morphology governs their spacing. Detailed electron microscopy analysis reveals that thin {111} sidewall facets, which elongate following the first twin boundary (TB1), are responsible for deforming the triple-phase line and favoring the formation of the second twin boundary (TB2).

Rational defect introduction in silicon nanowires.

The controlled introduction of planar defects, particularly twin boundaries and stacking faults, in group IV nanowires remains challenging despite the prevalence of these structural features in other nanowire systems (e.g., II-VI and III-V).

Tunable mid-infrared localized surface plasmon resonances in silicon nanowires.

We observe and systematically tune an intense mid-infrared absorption mode that results from phosphorus doping in silicon nanowires synthesized via the vapor-liquid-solid technique. The angle- and shape-dependence of this spectral feature, as determined via in-situ transmission infrared spectroscopy, supports its assignment as a longitudinal localized surface plasmon resonance (LSPR). Modulation of resonant frequency (740-1620 cm(-1)) is accomplished by varying nanowire length (135-1160 nm).

Chemical control of semiconductor nanowire kinking and superstructure.

We show that methylgermane (GeH(3)CH(3)) can induce a transition from 111 to 110 oriented growth during the vapor-liquid-solid synthesis of Ge nanowires. This hydride-based chemistry is subsequently leveraged to rationally fabricate kinking superstructures based on combinations of 111 and 110 segments. The addition of GeH(3)CH(3) also eliminates sidewall tapering and enables Ge nanowire growth at temperatures exceeding 475 °C, which greatly expands the process window and opens new avenues to create Si/Ge heterostructures.

Controlling silicon nanowire growth direction via surface chemistry.

We report on the first in situ chemical investigation of vapor-liquid-solid semiconductor nanowire growth and reveal the important, and previously unrecognized, role of transient surface chemistry near the triple-phase line. Real-time infrared spectroscopy measurements coupled with postgrowth electron microscopy demonstrate that covalently bonded hydrogen atoms are responsible for the (left angle bracket 111 right angle bracket) to (left angle bracket 112 right angle bracket) growth orientation transition commonly observed during Si nanowire growth. Our findings provide insight into the root cause of this well-known nanowire growth phenomenon and open a new route to rationally engineer the crystal structure of these nanoscale semi-conductors.