Sergiy Krylyuk

In situ atomic-scale imaging of electrochemical lithiation in silicon

In lithium-ion batteries, the electrochemical reaction between the electrodes and lithium is a critical process that controls the capacity, cyclability and reliability of the battery. Despite intensive study, the atomistic mechanism of the electrochemical reactions occurring in these solid-state electrodes remains unclear. Here, we show that in situ transmission electron microscopy can be used to study the dynamic lithiation process of single-crystal silicon with atomic resolution. We observe a sharp interface (~1 nm thick) between the crystalline silicon and an amorphous Li(x)Si alloy. The lithiation kinetics are controlled by the migration of the interface, which occurs through a ledge mechanism involving the lateral movement of ledges on the close-packed {111} atomic planes. Such ledge flow processes produce the amorphous Li(x)Si alloy through layer-by-layer peeling of the {111} atomic facets, resulting in the orientation-dependent mobility of the interfaces.

Tapering Control of Si Nanowires Grown from SiCl4 at Reduced Pressure

Device applications of tapered Si nanowire (SiNW) arrays require reliable technological approaches for fabricating nanowires with controlled shape and orientation. In this study, we systematically explore effects of growth conditions on tapering of Si nanowires grown by chemical vapor deposition (CVD) at reduced pressure from SiCl(4) precursor. Tapering of SiNWs is governed by the interplay between the catalyzed vapor-liquid-solid (VLS) and uncatalyzed vapor-solid (VS) growth mechanisms. We found that the uncatalyzed Si deposition on NW sidewalls, defined by a radial growth rate, can be enhanced by lowering SiCl(4)/H(2) molar ratio, applying higher gas flow rate, or reducing growth pressure. Distinct dependences of the axial and radial growth rates on the process conditions were employed to produce SiNWs with a tapering degree (i.e., a ratio of the radial/axial growth rates) varying by almost 2 orders of magnitude. The results are explained by an interplay between the thermodynamic and kinetic effects on the axial (VLS) and radial (VS) growth rates. Established correlation between the SiCl(4)/H(2) molar ratio and vertical alignment of nanowires was used to develop a two-stage growth procedure for producing tapered SiNW arrays with a predominantly vertical orientation.

Ultimate bending strength of Si nanowires.

Test platforms for the ideal strength of materials are provided by almost defect-free nanostructures (nanowires, nanotubes, nanoparticles, for example). In this work, the ultimate bending strengths of Si nanowires with radii in the 20-60 nm range were investigated by using a new bending protocol. Nanowires simply held by adhesion on flat substrates were bent through sequential atomic force microscopy manipulations. The bending states prior to failure were analyzed in great detail to measure the bending dynamics and the ultimate fracture strength of the investigated nanowires. An increase in the fracture strengths from 12 to 18 GPa was observed as the radius of nanowires was decreased from 60 to 20 nm. The large values of the fracture strength of these nanowires, although comparable with the ideal strength of Si, are explained in terms of the surface morphology of the nanowires.

Surface effects on the elastic modulus of Te nanowires

Nondestructive elastic property measurements have been performed on Te nanowires with diameters in the range 20–150nm. By using contact resonance atomic force microscopy, the elastic indentation modulus perpendicular to the prismatic facets of the nanowires has been accurately quantified. In this diameter range, a pronounced size dependence of the modulus has been observed: an invariant value consistent with Te bulk properties for large wire diameters, followed by a nonlinear increase with decreasing diameter, and finally an almost doubling of the modulus for Te nanowires thinner than 30nm. A model based on surface stiffening describes the observations.

Electron Microscopy Observation of TiO2 Nanocrystal Evolution in High-Temperature Atomic Layer Deposition

Understanding the evolution of amorphous and crystalline phases during atomic layer deposition (ALD) is essential for creating high quality dielectrics, multifunctional films/coatings, and predictable surface functionalization. Through comprehensive atomistic electron microscopy study of ALD TiO2 nanostructures at designed growth cycles, we revealed the transformation process and sequence of atom arrangement during TiO2 ALD growth. Evolution of TiO2 nanostructures in ALD was found following a path from amorphous layers to amorphous particles to metastable crystallites and ultimately to stable crystalline forms. Such a phase evolution is a manifestation of the Ostwald-Lussac Law, which governs the advent sequence and amount ratio of different phases in high-temperature TiO2 ALD nanostructures. The amorphous-crystalline mixture also enables a unique anisotropic crystal growth behavior at high temperature forming TiO2 nanorods via the principle of vapor-phase oriented attachment.

Compressive Stress Effect on the Radial Elastic Modulus of Oxidized Si Nanowires

Detailed understanding and optimal control of the properties of Si nanowires are essential steps in developing Si nanoscale circuitry. In this work, we have investigated mechanical properties of as-grown and oxidized Si nanowires as a function of their diameter. From contact-resonance atomic force microscopy measurements, the effect of the compressive stress at the Si-SiO(2) interface was revealed in the diameter dependence of the elastic modulus of Si nanowires oxidized at 900 and 1000 degrees C. A modified core-shell model that includes the interface stress developed during oxidation captures the diameter dependence observed in the measured elastic moduli of these oxidized Si nanowires. The values of strain and stress as well as the width of the stressed transition region at the Si-SiO(2) interface agree with those reported in simulations and experiments.

Rapid thermal oxidation of silicon nanowires

Oxidation kinetics of silicon nanowires (SiNWs) subjected to rapid thermal oxidation (RTO) at 900 °C and 1000 °C in dry oxygen for exposure times ranging from 1 to 7.5 min is reported. For 1 min, SiNWs exhibit an enhanced oxidation rate compared to planar silicon, but for longer exposures the oxidation rates of SiNWs and planar Si are similar. Compared to furnace oxidation of SiNWs, RTO provides faster average oxidation rates and a weaker dependence of oxide shell thickness on the NW diameter. Our results demonstrate that RTO is an efficient approach for controlled oxidation of SiNWs.

Formation of large-area GaN nanostructures with controlled geometry and morphology using top-down fabrication scheme

This paper details the fabrication of GaN nanoscale structures using deep ultraviolet lithography and inductively coupled plasma (ICP) etching techniques. The authors controlled the geometry (dimensions and shape) and surface morphology of such nanoscale structures through selection of etching parameters. The authors compared seven different chlorine-based etch chemistries: Cl2, Ar, Cl2/N2, Cl2/Ar, Cl2/N2/Ar, Cl2/H2/Ar, and Cl2/He/Ar. The authors found that nitrogen plays a significant role in fabricating high quality etched GaN nanostructures. This paper presents the effects of varying the etch parameters, including gas chemistry, gas flow rate, ICP power, rf power, chamber pressure, and substrate temperature, on the etch characteristics, including etch rate, sidewall angle, anisotropy, mask erosion, and surface roughness. Dominant etch mechanisms in relation to the observed characteristics of the etched features are discussed. Utilizing such methods, the authors demonstrated the fabrication of nanoscale...

Contact-resonance atomic force microscopy for nanoscale elastic property measurements: Spectroscopy and imaging

Quantitative measurements of the elastic modulus of nanosize systems and nanostructured materials are provided with great accuracy and precision by contact-resonance atomic force microscopy (CR-AFM). As an example of measuring the elastic modulus of nanosize entities, we used the CR-AFM technique to measure the out-of-plane indentation modulus of tellurium nanowires. A size-dependence of the indentation modulus was observed for the investigated tellurium nanowires with diameters in the range 20-150nm. Over this diameter range, the elastic modulus of the outer layers of the tellurium nanowires experienced significant enhancement due to a pronounced surface stiffening effect. Quantitative estimations for the elastic moduli of the outer and inner parts of tellurium nanowires of reduced diameter are made with a core-shell structure model. Besides localized elastic modulus measurements, we have also developed a unique CR-AFM imaging capability to map the elastic modulus over a micrometer-scale area. We used this CR-AFM capability to construct indentation modulus maps at the junction between two adjacent facets of a tellurium microcrystal. The clear contrast observed in the elastic moduli of the two facets indicates the different surface crystallography of these facets.

Correlation between the performance and microstructure of Ti/Al/Ti/Au Ohmic contacts to p-type silicon nanowires

Understanding the electrical and microstructural aspects of contact formation at nanoscale is essential for the realization of low-resistance metallization suitable for the next generation of nanowire based devices. In this study, we present detailed electrical and microstructural characteristics of Ti/Al/Ti/Au metal contacts to p-type Si nanowires (SiNWs) annealed at various temperatures. Focused ion beam cross-sectioning techniques and scanning transmission electron microscopy (STEM) were used to determine the microstructure of the source/drain metal contacts of working SiNW field-effect transistors (FETs) annealed for 30 s in the 450-850 °C temperature range in inert atmosphere. Formation of titanium silicides is observed at the metal/semiconductor interface after the 750 °C anneal. Extensive Si out-diffusion from the nanowire after the 750 °C anneal led to Kirkendall void formation. Annealing at 850 °C led to almost complete out-diffusion of Si from the nanowire core. Devices with 550 °C annealed contacts had linear electrical characteristics; whereas the devices annealed at 750 °C had the best characteristics in terms of linearity, symmetric behavior, and yield. Devices annealed at 850 °C had poor yield, which can be directly attributed to the microstructure of the contact region observed in STEM.