1-D Metal Nanobead Arrays within Encapsulated Nanowires via a Red-Ox-Induced Dewetting: Mechanism Study by Atom-Probe Tomography.

Metal nanoparticle arrays are excellent candidates for a variety of applications due to the versatility of their morphology and structure at the nanoscale. Bottom-up self-assembly of metal nanoparticles provides an important complementary alternative to the traditional top-down lithography method and makes it possible to assemble structures with higher-order complexity, for example, nanospheres, nanocubes, and core-shell nanostructures. Here we present a mechanism study of the self-assembly process of 1-D noble metal nanoparticles arrays, composed of Au, Ag, and AuAg alloy nanoparticles. These are prepared within an encapsulated germanium nanowire, obtained by the oxidation of a metal-germanium nanowire hybrid structure. The resulting structure is a 1-D array of equidistant metal nanoparticles with the same diameter, the so-called nanobead (NB) array structure. Atom-probe tomography and transmission electron microscopy were utilized to investigate the details of the morphological and chemical evolution during the oxidation of the encapsulated metal-germanium nanowire hybrid-structures. The self-assembly of nanoparticles relies on the formation of a metal-germanium liquid alloy and the migration of the liquid alloy into the nanowire, followed by dewetting of the liquid during shape-confined oxidation where the liquid column breaks-up into nanoparticles due to the Plateau-Rayleigh instability. Our results demonstrate that the encapsulating oxide layer serves as a structural scaffold, retaining the overall shape during the eutectic liquid formation and demonstrates the relationship between the oxide mechanical properties and the final structural characteristics of the 1-D arrays. The mechanistic details revealed here provide a versatile tool-box for the bottom-up fabrication of 1-D arrays nanopatterning that can be modified for multiple applications according to the RedOx properties of the material system components.

Direct Dopant Patterning by a Remote Monolayer Doping Enabled by a Monolayer Fragmentation Study.

The development of new doping methods extending beyond the traditional and well-established techniques is desired to match the rapid advances made in semiconductor (SC)-processing methods and nanostructure synthesis in numerous emerging applications, including the doping of 3D architectures. To address this, monolayer doping (MLD) and monolayer contact doping methods have been introduced recently. The MLD methods enable separation of the doping process of nanostructures from the synthesis step; hence, it is termed ex situ doping. Here, we present a new ex situ MLD method termed remote MLD (R-MLD). The noncontact doping method is based on the thermal fragmentation of dopant-containing monolayers and evaporation processes taking place during annealing of the uncapped monolayer dopant source positioned in proximity, however, without making physical contact with the target SC surface. We present a two-step annealing procedure that allows the study of the dopant monolayer fragmentation and evaporation stages and quantification of the doping levels obtained during each step. We demonstrate the application of R-MLD for achieving a large-scale direct patterning of silicon substrates with sharp doping profiles. The direct dopant patterning is obtained without applying lithographic processing steps to the target substrate. The noncontact doping process, monolayer decomposition, and fragment evaporation were studied using thermogravimetric analysis coupled with mass spectrometry and sheet resistance measurements. The doped patterns were characterized using scanning electron microscopy, scanning capacitance microscopy, and time-of-flight secondary ion mass spectroscopy.

Dopant Diffusion and Activation in Silicon Nanowires Fabricated by ex Situ Doping: A Correlative Study via Atom-Probe Tomography and Scanning Tunneling Spectroscopy.

Dopants play a critical role in modulating the electric properties of semiconducting materials, ranging from bulk to nanoscale semiconductors, nanowires, and quantum dots. The application of traditional doping methods developed for bulk materials involves additional considerations for nanoscale semiconductors because of the influence of surfaces and stochastic fluctuations, which may become significant at the nanometer-scale level. Monolayer doping is an ex situ doping method that permits the post growth doping of nanowires. Herein, using atom-probe tomography (APT) with subnanometer spatial resolution and atomic-ppm detection limit, we study the distributions of boron and phosphorus in ex situ doped silicon nanowires with accurate control. A highly phosphorus doped outer region and a uniformly boron doped interior are observed, which are not predicted by criteria based on bulk silicon. These phenomena are explained by fast interfacial diffusion of phosphorus and enhanced bulk diffusion of boron, respectively. The APT results are compared with scanning tunneling spectroscopy data, which yields information concerning the electrically active dopants. Overall, comparing the information obtained by the two methods permits us to evaluate the diffusivities of each different dopant type at the nanowire oxide, interface, and core regions. The combined data sets permit us to evaluate the electrical activation and compensation of the dopants in different regions of the nanowires and understand the details that lead to the sharp p-i-n junctions formed across the nanowire for the ex situ doping process.

Semiconductor-Metal Nanofloret Hybrid Structures by Self-Processing Synthesis.

We present a synthetic strategy that takes advantage of the inherent asymmetry exhibited by semiconductor nanowires prepared by Au-catalyzed chemical vapor deposition (CVD). The metal-semiconductor junction is used for activating etch, deposition, and modification steps localized to the tip area using a wet-chemistry approach. The hybrid nanostructures obtained for the coinage metals Cu, Ag, and Au resemble the morphology of grass flowers, termed here Nanofloret hybrid nanostructures consisting of a high aspect ratio SiGe nanowire (NW) with a metallic nanoshell cap. The synthetic method is used to prepare hybrid nanostructures in one step by triggering a programmable cascade of events that is autonomously executed, termed self-processing synthesis. The synthesis progression was monitored by ex situ transmission electron microscopy (TEM), in situ scanning transmission electron microscopy (STEM) and inductively coupled plasma mass spectrometry (ICP-MS) analyses to study the mechanistic reaction details of the various processes taking place during the synthesis. Our results indicate that the synthesis involves distinct processing steps including localized oxide etch, metal deposition, and process termination. Control over the deposition and etching processes is demonstrated by several parameters: (i) etchant concentration (water), (ii) SiGe alloy composition, (iii) reducing agent, (iv) metal redox potential, and (v) addition of surfactants for controlling the deposited metal grain size. The NF structures exhibit broad plasmonic absorption that is utilized for demonstrating surface-enhanced Raman scattering (SERS) of thiophenol monolayer. The new type of nanostructures feature a metallic nanoshell directly coupled to the crystalline semiconductor NW showing broad plasmonic absorption.

Criteria and considerations for preparing atom-probe tomography specimens of nanomaterials utilizing an encapsulation methodology.

Atom-probe tomography (APT) is a powerful method for characterization of nanomaterials due to its atomic-ppm level detection limit and Angstrom spatial resolution. Sample preparation for nanomaterials is, however, challenging because of their small dimensions and complicated geometries. Nanowires, with their high geometrical aspect ratio and nanowire length, 10 to 100 times their typical diameters, are highly suitable specimens for APT analyses, which can be transferred to silicon microposts using a nanomanipulator for direct APT measurements. This method is, however, prone to poor alignment and a limited field-of-view (FOV). Most importantly, direct implementation of APT with high aspect ratio nanowires may yield a low success rate of ∼30%, due to the high electric fields (10-40 V nm-1) associated with APT. While this is acceptable for samples analyzed solely by APT, a low sample yield makes it challenging to perform correlative experiments on the same nanowire specimen, utilizing other sophisticated characterization instruments. Herein, we introduce a general strategy for preparing high-yield APT specimens by encapsulating the nanowires utilizing a conformal atomic-layer deposition (ALD) coating followed by site-specific lift-out using a dual-beam focused-ion beam microscope. The ALD deposited coating forms strong chemical bonds with the Si nanowires yielding a high-quality and robust interface. The evaporation electric fields of the ALD coating and the nanowires are tuned by changing laser energy to obtain a uniform evaporation rate. The strong adhesion of the ALD-coating/nanowire interface and uniform evaporation rate produce a >90% specimen yield, with small concentration of reconstruction artifacts in 3-D. Simultaneously, the field-of-view is enhanced and the surface of the nanowire becomes visible, which makes the study of surface adsorption, segregation and oxidation possible. We utilized ALD-ZnO coated silicon nanowires as an example for investigating the criteria for choosing coating materials, laser pulse energy, laser direction, sample geometry, and substrate materials. The same criteria and considerations are applicable for preparing specimens of nanoparticles and 2-D material.

Tailor-made oxide architectures attained by molecularly permeable metal-oxide organic hybrid thin films.

Tailor-made metal oxide (MO) thin films with controlled compositions, electronic structures, and architectures are obtained via molecular layer deposition (MLD) and solution treatment. Step-wise formation of permeable hybrid films by MLD followed by chemical modification in solution benefits from the versatility of gas phase reactivity on surfaces while maintaining flexibility which is more common at the liquid phase.

Parallel p-n junctions across nanowires by one-step ex situ doping.

The bottom-up synthesis of nanoscale building blocks is a versatile approach for the formation of a vast array of materials with controlled structures and compositions. This approach is one of the main driving forces for the immense progress in materials science and nanotechnology witnessed over the past few decades. Despite the overwhelming advances in the bottom-up synthesis of nanoscale building blocks and the fine control of accessible compositions and structures, certain aspects are still lacking. In particular, the transformation of symmetric nanostructures to asymmetric nanostructures by highly controlled processes while preserving the modified structural orientation still poses a significant challenge. We present a one-step ex situ doping process for the transformation of undoped silicon nanowires (i-Si NWs) to p-type/n-type (p-n) parallel p-n junction configuration across NWs. The vertical p-n junctions were measured by scanning tunneling microscopy (STM) in concert with scanning tunneling spectroscopy (STS), termed STM/S, to obtain the spatial electronic properties of the junction formed across the NWs. Additionally, the parallel p-n junction configuration was characterized by off-axis electron holography in a transmission electron microscope to provide an independent verification of junction formation. The doping process was simulated to elucidate the doping mechanisms involved in the one-step p-i-n junction formation.

Monolayer contact doping of silicon surfaces and nanowires using organophosphorus compounds.

Monolayer Contact Doping (MLCD) is a simple method for doping of surfaces and nanostructures(1). MLCD results in the formation of highly controlled, ultra shallow and sharp doping profiles at the nanometer scale. In MLCD process the dopant source is a monolayer containing dopant atoms. In this article a detailed procedure for surface doping of silicon substrate as well as silicon nanowires is demonstrated. Phosphorus dopant source was formed using tetraethyl methylenediphosphonate monolayer on a silicon substrate. This monolayer containing substrate was brought to contact with a pristine intrinsic silicon target substrate and annealed while in contact. Sheet resistance of the target substrate was measured using 4 point probe. Intrinsic silicon nanowires were synthesized by chemical vapor deposition (CVD) process using a vapor-liquid-solid (VLS) mechanism; gold nanoparticles were used as catalyst for nanowire growth. The nanowires were suspended in ethanol by mild sonication. This suspension was used to dropcast the nanowires on silicon substrate with a silicon nitride dielectric top layer. These nanowires were doped with phosphorus in similar manner as used for the intrinsic silicon wafer. Standard photolithography process was used to fabricate metal electrodes for the formation of nanowire based field effect transistor (NW-FET). The electrical properties of a representative nanowire device were measured by a semiconductor device analyzer and a probe station.

Transformation of organic-inorganic hybrid films obtained by molecular layer deposition to photocatalytic layers with enhanced activity.

We present the transformation of organic-inorganic hybrid titanicone films formed by TiCl(4) as metal precursor and ethylene glycol (EG) using solvent-free MLD to highly active photocatalytic films. The photocatalytic activities of the films were investigated using hydroxyl-functionalized porphyrin as a spectroscopic marker. TEM imaging and electron diffraction, XPS, UV-vis spectroscopy, and spectroscsopic ellipsometry were employed for structural and composition analyses of the films. The photocatalytic activity of Ti-EG films was investigated for different anneal temperatures and compared to TiO(2) films prepared by ALD using TiCl(4) as metal precursor and H(2)O (TiO(2) films). Overall, our results indicate that the photocatalytic activity of the thermally annealed Ti-EG film is about 5-fold increased compared to that of the TiO(2) film prepared by ALD for optimal process conditions. The combined results indicate that the structural and photocatalytic properties can be assigned to three states: (I) amorphous state, intermediate dye loading, low photocatalytic activity, (II) intermediate film state with both crystalline and amorphous regions, high dye loading, high catalytic activity, and (III) highly crystalline film with low dye loading and low photocatalytic activity. The formation of photocatalytic nanotubes (NTs) is demonstrated using sacrificial Ge nanowires (NWs) scaffolds to yield Ti-EG NT structures with controllable wall thickness structures and enhanced dye loading capacity. Our results demonstrate the feasibility and high potential of MLD to form metal oxides with high photocatalytic activity.

Contact doping of silicon wafers and nanostructures with phosphine oxide monolayers.

Contact doping method for the controlled surface doping of silicon wafers and nanometer scale structures is presented. The method, monolayer contact doping (MLCD), utilizes the formation of a dopant-containing monolayer on a donor substrate that is brought to contact and annealed with the interface or structure intended for doping. A unique feature of the MLCD method is that the monolayer used for doping is formed on a separate substrate (termed donor substrate), which is distinct from the interface intended for doping (termed acceptor substrate). The doping process is controlled by anneal conditions, details of the interface, and molecular precursor used for the formation of the dopant-containing monolayer. The MLCD process does not involve formation and removal of SiO(2) capping layer, allowing utilization of surface chemistry details for tuning and simplifying the doping process. Surface contact doping of intrinsic Si wafers (i-Si) and intrinsic silicon nanowires (i-SiNWs) is demonstrated and characterized. Nanowire devices were formed using the i-SiNW channel and contact doped using the MLCD process, yielding highly doped SiNWs. Kelvin probe force microscopy (KPFM) was used to measure the longitudinal dopant distribution of the SiNWs and demonstrated highly uniform distribution in comparison with in situ doped wires. The MLCD process was studied for i-Si substrates with native oxide and H-terminated surface for three types of phosphorus-containing molecules. Sheet resistance measurements reveal the dependency of the doping process on the details of the surface chemistry used and relation to the different chemical environments of the P═O group. Characterization of the thermal decomposition of several monolayer types formed on SiO(2) nanoparticles (NPs) using TGA and XPS provides insight regarding the role of phosphorus surface chemistry at the SiO(2) interface in the overall MLCD process. The new MLCD process presented here for controlled surface doping provides a simple yet highly versatile means for achieving postgrowth doping of nanometer scale structures and interfaces.