Silicon nanowire degradation and stabilization during lithium cycling by SEI layer formation.

Silicon anodes are of great interest for advanced lithium-ion battery applications due to their order of magnitude higher energy capacity than graphite. Below a critical diameter, silicon nanowires enable the ∼300% volume expansion during lithiation without pulverization. However, their high surface-to-volume ratio is believed to contribute to fading of their capacity retention during cycling due to solid-electrolyte-interphase (SEI) growth on surfaces. To better understand this issue, previous studies have examined the composition and morphology of the SEI layers. Here we report direct measurements of the reduction in silicon nanowire diameter with number of cycles due to SEI formation. The results reveal significantly greater Si loss near the nanowire base. From the change in silicon volume we can accurately predict the measured specific capacity reduction for silicon nanowire half cells. The enhanced Si loss near the nanowire/metal current collector interface suggests new strategies for stabilizing nanowires for long cycle life performance.

Diameter-independent hole mobility in Ge/Si core/shell nanowire field effect transistors.

Heterostructure engineering capability, especially in the radial direction, is a unique property of bottom-up nanowires (NWs) that makes them a serious candidate for high-performance field-effect transistors (FETs). In this Letter, we present a comprehensive study on size dependent carrier transport behaviors in vapor-liquid-solid grown Ge/Si core/shell NWFETs. Transconductance, subthreshold swing, and threshold voltage exhibit a linear increase with the NW diameter due to the increase of the transistor body size. Carrier confinement in this core/shell architecture is shown to maintain a diameter-independent hole mobility as opposed to surface-induced mobility degradation in homogeneous Ge NWs. The Si shell thickness also exhibits a slight effect on the hole mobility, while the most abrupt mobility transition is between structures with and without the Si shell. A hole mobility of 200 cm(2)/(V · s) is extracted from transistor performance for core/shell NWs with a diameter range of 15-50 nm and a 3 nm Si shell. The constant mobility enables a complete and unambiguous dependence of FET performance on NW diameter to be established and provides a caliper for performance comparisons between NWFETs and with other FET families.

Size-dependent silicon epitaxy at mesoscale dimensions.

New discoveries on collective processes in materials fabrication and performance are emerging in the mesoscopic size regime between the nanoscale, where atomistic effects dominate, and the macroscale, where bulk-like behavior rules. For semiconductor electronics and photonics, dimensional control of the architecture in this regime is the limiting factor for device performance. Epitaxial crystal growth is the major tool enabling simultaneous control of the dimensions and properties of such architectures. Although size-dependent effects have been studied for many small-scale systems, they have not been reported for the epitaxial growth of Si crystalline surfaces. Here, we show a strong dependence of epitaxial growth rates on size for nano to microscale radial wires and planar stripes. A model for this unexpected size-dependent vapor phase epitaxy behavior at small dimensions suggests that these effects are universal and result from an enhanced surface desorption of the silane (SiH4) growth precursor near facet edges. Introducing phosphorus or boron dopants during the silicon epitaxy further decreases the growth rates and, for phosphorus, gives rise to a critical layer thickness for single crystalline epitaxial growth. This previously unknown mesoscopic size-dependent growth effect at mesoscopic dimensions points to a new mechanism in vapor phase growth and promises greater control of advanced device geometries.

Enhanced lithium ion battery cycling of silicon nanowire anodes by template growth to eliminate silicon underlayer islands.

It is well-known that one-dimensional nanostructures reduce pulverization of silicon (Si)-based anode materials during Li ion cycling because they allow lateral relaxation. However, even with improved designs, Si nanowire-based structures still exhibit limited cycling stability for extended numbers of cycles, with the specific capacity retention with cycling not showing significant improvements over commercial carbon-based anode materials. We have found that one important reason for the lack of long cycling stability can be the presence of milli- and microscale Si islands which typically form under nanowire arrays during their growth. Stress buildup in these Si island underlayers with cycling results in cracking, and the loss of specific capacity for Si nanowire anodes, due to progressive loss of contact with current collectors. We show that the formation of these parasitic Si islands for Si nanowires grown directly on metal current collectors can be avoided by growth through anodized aluminum oxide templates containing a high density of sub-100 nm nanopores. Using this template approach we demonstrate significantly enhanced cycling stability for Si nanowire-based lithium-ion battery anodes, with retentions of more than ~1000 mA·h/g discharge capacity over 1100 cycles.

Nucleation and atomic layer reaction in nickel silicide for defect-engineered Si nanochannels.

At the nanoscale, defects can significantly impact phase transformation processes and change materials properties. The material nickel silicide has been the industry standard electrical contact of silicon microelectronics for decades and is a rich platform for scientific innovation at the conjunction of materials and electronics. Its formation in nanoscale silicon devices that employ high levels of strain, intentional, and unintentional twins or grain boundaries can be dramatically different from the commonly conceived bulk processes. Here, using in situ high-resolution transmission electron microscopy (HRTEM), we capture single events during heterogeneous nucleation and atomic layer reaction of nickel silicide at various crystalline boundaries in Si nanochannels for the first time. We show through systematic experiments and analytical modeling that unlike other typical face-centered cubic materials such as copper or silicon the twin defects in NiSi2 have high interfacial energies. We observe that these twin defects dramatically change the behavior of new phase nucleation and can have direct implications for ultrascaled devices that are prone to defects or may utilize them to improve device performance.

Gold catalyzed nickel disilicide formation: a new solid-liquid-solid phase growth mechanism.

The vapor-liquid-solid (VLS) mechanism is the predominate growth mechanism for semiconductor nanowires (NWs). We report here a new solid-liquid-solid (SLS) growth mechanism of a silicide phase in Si NWs using in situ transmission electron microcopy (TEM). The new SLS mechanism is analogous to the VLS one in relying on a liquid-mediating growth seed, but it is fundamentally different in terms of nucleation and mass transport. In SLS growth of Ni disilicide, the Ni atoms are supplied from remote Ni particles by interstitial diffusion through a Si NW to the pre-existing Au-Si liquid alloy drop at the tip of the NW. Upon supersaturation of both Ni and Si in Au, an octahedral nucleus of Ni disilicide (NiSi2) forms at the center of the Au liquid alloy, which thereafter sweeps through the Si NW and transforms Si into NiSi2. The dissolution of Si by the Au alloy liquid mediating layer proceeds with contact angle oscillation at the triple point where Si, oxide of Si, and the Au alloy meet, whereas NiSi2 is grown from the liquid mediating layer in an atomic stepwise manner. By using in situ quenching experiments, we are able to measure the solubility of Ni and Si in the Au-Ni-Si ternary alloy. The Au-catalyzed mechanism can lower the formation temperature of NiSi2 by 100 °C compared with an all solid state reaction.

Tailoring lithiation behavior by interface and bandgap engineering at the nanoscale.

Controlling the transport of lithium (Li) ions and their reaction with electrodes is central in the design of Li-ion batteries for achieving high capacity, high rate, and long lifetime. The flexibility in composition and structure enabled by tailoring electrodes at the nanoscale could drastically change the ionic transport and help meet new levels of Li-ion battery performance. Here, we demonstrate that radial heterostructuring can completely suppress the commonly observed surface insertion of Li ions in all reported nanoscale systems to date and to exclusively induce axial lithiation along the [111] direction in a layer-by-layer fashion. The new lithiation behavior is achieved through the deposition of a conformal, epitaxial, and ultrathin silicon (Si) shell on germanium (Ge) nanowires, which creates an effective chemical potential barrier for Li ion diffusion through and reaction at the nanowire surface, allowing only axial lithiation and volume expansion. These results demonstrate for the first time that interface and bandgap engineering of electrochemical reactions can be utilized to control the nanoscale ionic transport/insertion paths and thus may be a new tool to define the electrochemical reactions in Li-ion batteries.

Direct measurement of coherency limits for strain relaxation in heteroepitaxial core/shell nanowires.

The growth of heteroepitaxially strained semiconductors at the nanoscale enables tailoring of material properties for enhanced device performance. For core/shell nanowires (NWs), theoretical predictions of the coherency limits and the implications they carry remain uncertain without proper identification of the mechanisms by which strains relax. We present here for the Ge/Si core/shell NW system the first experimental measurement of critical shell thickness for strain relaxation in a semiconductor NW heterostructure and the identification of the relaxation mechanisms. Axial and tangential strain relief is initiated by the formation of periodic a/2 <110> perfect dislocations via nucleation and glide on {111} slip-planes. Glide of dislocation segments is directly confirmed by real-time in situ transmission electron microscope observations and by dislocation dynamics simulations. Further shell growth leads to roughening and grain formation which provides additional strain relief. As a consequence of core/shell strain sharing in NWs, a 16 nm radius Ge NW with a 3 nm Si shell is shown to accommodate 3% coherent strain at equilibrium, a factor of 3 increase over the 1 nm equilibrium critical thickness for planar Si/Ge heteroepitaxial growth.

Silicon nanowires: electron holography studies of doped p-n junctions and biased Schottky barriers.

We report an in situ examination of individual Si p-n junction nanowires (NWs) using off-axis electron holography (EH) during transmission electron microscopy. The SiNWs were synthesized by chemical vapor deposition with an axial dopant profile from n- to p-type, and then placed inside the transmission electron microscope as a cantilever geometry in contact with a movable Pt probe for in situ biasing measurements during simultaneous EH observations. The phase shift from EH indicates the potential shift between the p- and n-segments to be 1.03 ± 0.17 V due to the built-in voltage. The I-V characteristics of a single SiNW indicate the formation of a Schottky barrier between the NW tip and the movable Pt contact. EH observations show a strong concentration of electric field at this contact, preventing a change in the Si energy bands in the p-n junction region due to the applied bias.

Ultrashort channel silicon nanowire transistors with nickel silicide source/drain contacts.

We demonstrate the shortest transistor channel length (17 nm) fabricated on a vapor-liquid-solid (VLS) grown silicon nanowire (NW) by a controlled reaction with Ni leads on an in situ transmission electron microscope (TEM) heating stage at a moderate temperature of 400 °C. NiSi(2) is the leading phase, and the silicide-silicon interface is an atomically sharp type-A interface. At such channel lengths, high maximum on-currents of 890 (µA/µm) and a maximum transconductance of 430 (µS/µm) were obtained, which pushes forward the performance of bottom-up Si NW Schottky barrier field-effect transistors (SB-FETs). Through accurate control over the silicidation reaction, we provide a systematic study of channel length dependent carrier transport in a large number of SB-FETs with channel lengths in the range of 17 nm to 3.6 µm. Our device results corroborate with our transport simulations and reveal a characteristic type of short channel effects in SB-FETs, both in on- and off-state, which is different from that in conventional MOSFETs, and that limits transport parameter extraction from SB-FETs using conventional field-effect transconductance measurements.

Lithium-assisted electrochemical welding in silicon nanowire battery electrodes.

From in situ transmission electron microscopy (TEM) observations, we present direct evidence of lithium-assisted welding between physically contacted silicon nanowires (SiNWs) induced by electrochemical lithiation and delithiation. This electrochemical weld between two SiNWs demonstrates facile transport of lithium ions and electrons across the interface. From our in situ observations, we estimate the shear strength of the welded region after delithiation to be approximately 200 MPa, indicating that a strong bond is formed at the junction of two SiNWs. This welding phenomenon could help address the issue of capacity fade in nanostructured silicon battery electrodes, which is typically caused by fracture and detachment of active materials from the current collector. The process could provide for more robust battery performance either through self-healing of fractured components that remain in contact or through the formation of a multiconnected network architecture.

Reversible nanopore formation in Ge nanowires during lithiation-delithiation cycling: an in situ transmission electron microscopy study.

Retaining the high energy density of rechargeable lithium ion batteries depends critically on the cycle stability of microstructures in electrode materials. We report the reversible formation of nanoporosity in individual germanium nanowires during lithiation-delithiation cycling by in situ transmission electron microscopy. Upon lithium insertion, the initial crystalline Ge underwent a two-step phase transformation process: forming the intermediate amorphous Li(x)Ge and final crystalline Li(15)Ge(4) phases. Nanopores developed only during delithiation, involving the aggregation of vacancies produced by lithium extraction, similar to the formation of porous metals in dealloying. A delithiation front was observed to separate a dense nanowire segment of crystalline Li(15)Ge(4) with a porous spongelike segment composed of interconnected ligaments of amorphous Ge. This front sweeps along the wire with a logarithmic time law. Intriguingly, the porous nanowires exhibited fast lithiation/delithiation rates and excellent mechanical robustness, attributed to the high rate of lithium diffusion and the porous network structure for facile stress relaxation, respectively. These results suggest that Ge, which can develop a reversible nanoporous network structure, is a promising anode material for lithium ion batteries with superior energy capacity, rate performance, and cycle stability.

Ultrafast electrochemical lithiation of individual Si nanowire anodes.

Using advanced in situ transmission electron microscopy, we show that the addition of a carbon coating combined with heavy doping leads to record-high charging rates in silicon nanowires. The carbon coating and phosphorus doping each resulted in a 2 to 3 orders of magnitude increase in electrical conductivity of the nanowires that, in turn, resulted in a 1 order of magnitude increase in charging rate. In addition, electrochemical solid-state amorphization (ESA) and inverse ESA were directly observed and characterized during a two-step phase transformation process during lithiation: crystalline silicon (Si) transforming to amorphous lithium-silicon (Li(x)Si) which transforms to crystalline Li(15)Si(4) (capacity 3579 mAh·g(-1)). The ultrafast charging rate is attributed to the nanoscale diffusion length and the improved electron and ion transport. These results provide important insight in how to use Si as a high energy density and high power density anode in lithium ion batteries for electrical vehicle and other electronic power source applications.

Anisotropic swelling and fracture of silicon nanowires during lithiation.

We report direct observation of an unexpected anisotropic swelling of Si nanowires during lithiation against either a solid electrolyte with a lithium counter-electrode or a liquid electrolyte with a LiCoO(2) counter-electrode. Such anisotropic expansion is attributed to the interfacial processes of accommodating large volumetric strains at the lithiation reaction front that depend sensitively on the crystallographic orientation. This anisotropic swelling results in lithiated Si nanowires with a remarkable dumbbell-shaped cross section, which develops due to plastic flow and an ensuing necking instability that is induced by the tensile hoop stress buildup in the lithiated shell. The plasticity-driven morphological instabilities often lead to fracture in lithiated nanowires, now captured in video. These results provide important insight into the battery degradation mechanisms.

Si Radial p-i-n Junction Photovoltaic Arrays with Built-In Light Concentrators.

High-performance photovoltaic (PV) devices require strong light absorption, low reflection and efficient photogenerated carrier collection for high quantum efficiency. Previous optical studies of vertical wires arrays have revealed that extremely efficient light absorption in the visible wavelengths is achievable. Photovoltaic studies have further advanced the wire approach by employing radial p-n junction architectures to achieve more efficient carrier collection. While radial p-n junction formation and optimized light absorption have independently been considered, PV efficiencies have further opportunities for enhancement by exploiting the radial p-n junction fabrication procedures to form arrays that simultaneously enhance both light absorption and carrier collection efficiency. Here we report a concept of morphology control to improve PV performance, light absorption and quantum efficiency of silicon radial p-i-n junction arrays. Surface energy minimization during vapor phase epitaxy is exploited to form match-head structures at the tips of the wires. The match-head structure acts as a built-in light concentrator and enhances optical absorptance and external quantum efficiencies by 30 to 40%, and PV efficiency under AM 1.5G illumination by 20% compared to cylindrical structures without match-heads. The design rules for these improvements with match-head arrays are systematically studied. This approach of process-enhanced control of three-dimensional Si morphologies provides a fab-compatible way to enhance the PV performance of Si radial p-n junction wire arrays.

Catalyst composition and impurity-dependent kinetics of nanowire heteroepitaxy.

The mechanisms and kinetics of axial Ge-Si nanowire heteroepitaxial growth based on the tailoring of the Au catalyst composition via Ga alloying are studied by environmental transmission electron microscopy combined with systematic ex situ CVD calibrations. The morphology of the Ge-Si heterojunction, in particular, the extent of a local, asymmetric increase in nanowire diameter, is found to depend on the Ga composition of the catalyst, on the TMGa precursor exposure temperature, and on the presence of dopants. To rationalize the findings, a general nucleation-based model for nanowire heteroepitaxy is established which is anticipated to be relevant to a wide range of material systems and device-enabling heterostructures.

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.