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 SixGe1-x/SiyGe1-y 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. Efficient heat and mass transport also minimize the structural variations of nanowires grown in microcapsules with different diameters and wall thicknesses. Nanowires containing at least 16 segments and segment lengths below 75 nm are demonstrated.

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. The twisted nanotubes show large hollow cores and surprisingly high twisting rates, up to 9°/µm, that cannot be easily explained through the Eshelby twist model. A combination of ex situ and in situ transmission electron microscopy measurements suggest that the hollow core results from a competition between growth and etching at the Ge-ZnO interface during synthesis. The twisting rate is consistent with a softening of elastic rigidity. These results indicate that the use of unconventional, nonmetallic catalysts provides opportunities to synthesize unusual oxide nanostructures with potentially useful properties.

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 ZrO2on Si nanowires as a model system. Si nanowires are first grown with an axially modulated n-Si/i-Si dopant profile. SCALES then yields coaxial poly(methyl methacrylate) (PMMA) masks on the n-Si regions. Subsequent AS-ALD of ZrO2occurs on the exposed i-Si regions and not on those masked by PMMA. We show the spatial relationship between nanowire dopant profile, PMMA masks, and ZrO2films, confirming the programmability of the process. The nanoscale resolution of our process coupled with the plethora of available AS-ALD chemistries promises a range of future opportunities to generate structurally complex nanoscale materials and electronic devices using entirely bottom-up methods.

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. This analysis combines experimental measurements and computational simulations to determine the electrical conductivity of the nominally undoped segment of two-segment Si nanowires, as well as the ratio of the segment lengths. The efficacy of this approach is demonstrated by comparing results generated by EOS with conventional four-point-probe measurements. This work provides new insights into the control and variability of semiconductor nanowires for electronic applications and is a critical first step toward the high-throughput interrogation of complete nanowire-based devices.

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. Modulating the delivery of growth species or conditions permits compositional and/or structural encoding. A range of materials and devices (e.g., for electronics, photonics, thermal transport, and bioprobes) have been produced by VLS growth, but plenty of challenges remain: many desirable structures cannot currently be made, and even for those structures that can be made, the parameter window-in terms of, e.g., temperatures and pressures-is often narrow. Moreover, we are quite far from ab initio determination of which growth conditions should be used or even if a desired structure is fundamentally achievable within the VLS framework. To fully understand the challenges and promises of VLS growth, the governing physicochemical processes must be explored and understood at the atomic scale. This final level of detail is being unraveled with the help of in situ characterization techniques. The picture that is emerging is of a highly dynamical process with several deeply interconnected and highly fundamental components that are difficult to detect with postgrowth ex situ interrogation. For example, recent in situ microscopy and spectroscopy studies have shown that the growth front can undergo cyclical reshaping involving dissolution as well as crystallization and that the state of the nanowire surface, which changes with growth conditions as a result of a competition between adsorption and desorption of passivating species, plays a crucial role in determining the transport to/from and the stability of the seed particle. The available in situ observations currently constitute a somewhat disparate list, but if they can be connected to each other and to the outstanding challenges, they promise meaningful advances in our understanding of VLS growth. In this Account, we review the state of the art regarding the atomic-scale thermodynamic and kinetic phenomena that control VLS growth. Rather than cataloging all of the outstanding contributions to the field, we give priority to in situ observations that have revealed unexpected effects as well as those that hint at incongruities in our current knowledge. As such, our discussion should be viewed as an opportunity to gain deeper understanding and control of the fundamental processes at play, which will be crucial in future scale-up efforts and expansion to completely new materials systems and application areas.

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. Maintenance of a supercooled catalyst with only hydrogen radical delivery confirms the centrality of sidewall chemistry. This work underscores the importance of the nanowire sidewall and its chemistry on catalyst state, identifies new methods to regulate catalyst composition, and provides synthetic strategies for subeutectic growth in other nanowire systems.

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. Experiments as a function of substrate temperature, etchant flow rate, and nanowire diameter support a solid-liquid-vapor (SLV) mechanism. An etch model with reaction at the liquid-vapor interface as the rate-limiting step is consistent with our experiments. These results identify a new mechanism to in situ tune the concentration of semiconductor atoms in the catalyst droplet.

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.e., during growth) to those after saturating the nanowire sidewall with hydrogen atoms. This method provides sub-monolayer chemical information at relevant reaction conditions while accounting for the heterogeneity of sidewall surface sites and their evolution during elongation. Our findings demonstrate that changes to surface bonding are critical to understand Ge nanowire synthesis and provide new guidelines for rationally selecting catalysts, forming heterostructures, and controlling dopant profiles.

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). Here we demonstrate how user-programmable changes to precursor pressure and growth temperature can rationally generate both transverse twin boundaries and angled stacking faults during the growth of <111> oriented Si nanowires. We leverage this new capability to demonstrate prototype defect superstructures. These findings yield important insight into the mechanism of defect generation in semiconductor nanowires and suggest new routes to engineer the properties of this ubiquitous semiconductor.

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 (NbS3). 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 NbS3 1D nanostructures, nanowires and nanoribbons, each with sub-ten nanometer diameter, tens of micrometers length, and distinct 1D morphology and growth orientation are demonstrated. Strategies to control the location, size, and morphology of growth, and extend the growth method to synthesize other transition metal trichalcogenides, NbSe3 and TiS3, as nanowires are demonstrated. Finally, the role of the Au-NaCl alloy catalyst in guiding VLS synthesis is described and the growth mechanism based on the relationships measured between structure (growth orientation, morphology, and dimensions) and growth conditions (catalyst volume and growth time) is discussed. These results introduce opportunities to expand the library of emerging 1D vdW materials to make use of their unique properties through controlled growth at nanoscale dimensions.

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.

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.

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). The observed frequency shift is consistent with Mie-Gans theory, which indicates electrically active dopant concentrations between 10(19) and 10(20) cm(-3). Our findings suggest new opportunities to confine light in this ubiquitous semiconductor and engineer the optical properties of nontraditional plasmonic materials.

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.e., porosity) dominates the reduction in effective thermal conductivity and is supplemented by increased phonon-boundary scattering. The relative contributions of both mechanisms depend on the details of the nanoscale morphology. Our findings provide valuable insights into the factors that govern thermal conduction in complex nanoscale materials.

Bottom-Up Masking of Si/Ge Surfaces and Nanowire Heterostructures via 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 via 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. We demonstrate the key features of and characterize the SCALES process with a series of model Si/Ge systems: Si and Ge wafers, Si and Ge nanowires, and Si/Ge heterostructure nanowires.

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. The platform provides a dynamic interface with tunable brush heights that extend up to 20 microns - two orders of magnitude thicker than standard brushes. The brushes are easily sculpted into micropatterned landscapes by photo-deactivation of the enzyme. Further, they provide a continuous source of megadalton hyaluronan or they can be covalently-stabilized to the surface. Stabilized brushes exhibit superb resistance to biofilms, yet are locally digested by fibroblasts. This brush technology provides opportunities in a range of arenas including regenerating tailorable biointerfaces for implants, wound healing or lubrication as well as fundamental studies of the glycocalyx and polymer physics.

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. Due to the enhanced near-field coupling between resonators, we find that the group velocities and propagation lengths for doped Si plasmonic resonators in intrinsic Si nanowires can be increased by up to an order of magnitude compared to the case of isotropic vacuum surroundings. We investigate the impact of resonator aspect ratio, doping, and spacing on waveguide performance, and we find that propagation lengths are maximized for large aspect ratios and high dopant concentrations at small spacings. To study these complex anisotropic systems, we develop a new analytical "absorption spectra" method to extract waveguide information from simple far-field absorption experiments (or simulations) of only two coupled resonators.

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. In addition to performance and economic considerations, phenomena unique to the nanoscale must guide the design of each unit operation and the overall process flow. We identify and discuss four key nanomanufacturing process design needs: (a) appropriately selected process break points, (b) synthesis techniques appropriate for large-scale manufacturing,

Formation of surface-bound acyl groups by reaction of acyl halides on ge(100)-2x1.

We have investigated the reaction of a series of acyl halides, including acetyl chloride, acetyl bromide, acetyl-d3 chloride, benzoyl chloride, and pivaloyl chloride, on Ge(100)-2x1 with multiple internal reflection infrared (MIR-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). Infrared spectra following saturation exposures of acetyl chloride and acetyl bromide to Ge(100)-2x1 at 310 K are nearly identical, both exhibiting strong nu(C=O) stretching peaks near 1685 cm-1 and no vibrational modes in the nu(Ge-H) region. These data provide strong evidence for the presence of a surface-bound acetyl group on Ge(100)-2x1, which results from a C-X dissociation reaction (where X=Cl, Br). For acetyl chloride, DFT calculations predict that the barrier to C-Cl dissociation is only 1 kcal/mol above a chlorine-bound precursor state and is considerably smaller than barriers leading to the [2+2] C=O cycloaddition and alpha-CH dissociation products. In addition to the C-X dissociation product, both infrared and photoelectron results point to the presence of a second structure for acetyl halides where the oxygen of the surface-bound acetyl group donates charge to a nearby surface atom. This interaction is not observed for benzoyl chloride and pivaloyl chloride.