Diversely Doped Uniform Silicon Nanotube Axial Heterostructures Enabled by "Dopant Reflection".

Here, we propose a novel method for the synthesis of extremely uniform, diversely doped silicon nanotube heterostructures. The method, comprising a simple two-step synthesis, exploits the use of a Ge nanowire sacrificial core upon which a multidoping axial pattern can be easily obtained, that is enclosed in an intrinsic Si shell. The Ge-Si core-shell structure is then heated to 750 °C, allowing the migration of dopant elements from the Ge core directly into the Si shell. Removal of the Ge core, via either wet or dry etch, does not impair the crystallinity of the Si shell nor its electrical characteristics, allowing for the formation of a multidoped axially patterned, conformal, and uniform Si nanotube. The precise dopant patterning allows for the extension of Si nanotube applications, which were unattainable because of the inability to precisely control the parameters and uniformity of the nanotubes while doping the structure simultaneously.

Self-Catalyzed Vertically Aligned Carbon Nanotube-Silicon Core-Shell Array for Highly Stable, High-Capacity Lithium-Ion Batteries.

Here, we report on the simple, catalyst-free preparation and application of carbon nanotube-silicon core-shell composite anodes on stainless steel. The stainless steel mesh structure acts as a self-catalyzing agent for the plasma-enhanced chemical vapor deposition (PECVD) growth of vertically aligned, dense, multiwalled carbon nanotube arrays. The carbon nanotube array then serves as a bed for silicon deposition by the decomposition of silane through chemical vapor deposition (CVD). This approach leads to the formation of highly conductive and stable composite anodes. Silicon deposition on the substrate is controlled in terms of the optimal silicon shell thickness, thus enhancing the performance of the cell. These extremely stable, binder-free composite electrodes were characterized as potential anodes in Li-ion batteries, exhibiting long cycle life (>700 cycles), high gravimetric capacity (>4000 mAh/gSi), low irreversible capacity (<10%), and high Coulombic efficiency (>99.5%). These composite anodes meet the requirements of Li-ion batteries for future portable electronics and electric vehicle applications.

Large-Scale Self-Catalyzed Spongelike Silicon Nano-Network-Based 3D Anodes for High-Capacity Lithium-Ion Batteries.

Here, we report on the large-scale one-step preparation, characterization, and application of three-dimensional spongelike silicon alloy composite anodes, based on the catalyst-free growth of porous silicon nanonetworks directly onto highly conductive and flexible open-structure stainless steel current collectors. By the use of a key hydrofluoric-acid-based chemical pretreatment process, the originally noncatalytic stainless steel matrix becomes nanoporous and highly self-catalytic, thus greatly promoting the formation of a silicon spongelike network at unexpectedly low growth temperatures, 380-460 °C. Modulation of this unique chemical pretreatment allows control over the morphology and loading properties of the resulting silicon network. The spongelike silicon network growth is capable of completely filling the openings of the three-dimensional stainless steel substrates, thus allowing full control over the active material loading, while conserving high mechanical and chemical stabilities. Furthermore, extremely high silicon loadings are reached because of the supercatalytic nanoporous nature of the chemically treated stainless steel substrates (0.5-20 mg/cm2). This approach leads to the realization of highly electrically conductive Si-stainless steel composite anodes, due to the formation of silicon-network-to-stainless-steel contact sections composed of highly conductive metal silicide alloys, thus improving the electrical interface and mechanical stability between the silicon active network and the highly conductive metal current collector. More importantly, our one-step cost-effective growth approach allows the large-scale preparation of highly homogeneous ultrathin binder-free anodes, up to 2 m long, using a home-built CVD setup. Finally, we made use of these novel anodes for the assembly of Li-ion batteries exhibiting stable cycle life (cycled for over 500 cycles with <50% capacity loss at 0.1 mA), high gravimetric capacity (>3500 mA h/gSi at 0.1 mA/cm2), low irreversible capacity (<10%), and high Coulombic efficiency (>99.5%). Notably, these Si spongelike composite anodes of novel architecture meet the requirements of lithium batteries for future portable and electric-vehicle applications.

Tissue-like Silicon Nanowires-Based Three-Dimensional Anodes for High-Capacity Lithium Ion Batteries.

Here, we report on the scalable synthesis and characterization of novel architecture three-dimensional (3D) high-capacity amorphous silicon nanowires (SiNWs)-based anodes with focus on studying their electrochemical degradation mechanisms. We achieved an unprecedented combination of remarkable performance characteristics, high loadings of 3-15 mAh/cm(2), a very low irreversible capacity (10% for the 3-4 mAh/cm(2) anodes), current efficiency greater than 99.5%, cycle stability (both in half cells and a LiFePO4 battery), a total capacity of 457 mAh/cm(2) over 204 cycles and fast charge-discharge rates (up to 2.7C at 20 mA/cm(2)). These SiNWs-based binder-free 3D anodes have been cycled for over 200 cycles, exhibiting a stable cycle life. Notably, it was found that the growth of the continuous SEI layer thickness, and its concomitant increase in resistivity, represents the major reason for the observed capacity loss of the SiNWs-based anodes. Importantly, these NWs-based anodes of novel architecture meet the requirements of lithium batteries for future portable, and electric-vehicle, applications.

Manipulating and Monitoring On-Surface Biological Reactions by Light-Triggered Local pH Alterations.

Significant research efforts have been dedicated to the integration of biological species with electronic elements to yield smart bioelectronic devices. The integration of DNA, proteins, and whole living cells and tissues with electronic devices has been developed into numerous intriguing applications. In particular, the quantitative detection of biological species and monitoring of biological processes are both critical to numerous areas of medical and life sciences. Nevertheless, most current approaches merely focus on the "monitoring" of chemical processes taking place on the sensing surfaces, and little efforts have been invested in the conception of sensitive devices that can simultaneously "control" and "monitor" chemical and biological reactions by the application of on-surface reversible stimuli. Here, we demonstrate the light-controlled fine modulation of surface pH by the use of photoactive molecularly modified nanomaterials. Through the use of nanowire-based FET devices, we showed the capability of modulating the on-surface pH, by intensity-controlled light stimulus. This allowed us simultaneously and locally to control and monitor pH-sensitive biological reactions on the nanodevices surfaces, such as the local activation and inhibition of proteolytic enzymatic processes, as well as dissociation of antigen-antibody binding interactions. The demonstrated capability of locally modulating the on-surface effective pH, by a light stimuli, may be further applied in the local control of on-surface DNA hybridization/dehybridization processes, activation or inhibition of living cells processes, local switching of cellular function, local photoactivation of neuronal networks with single cell resolution and so forth.

Optically-gated self-calibrating nanosensors: monitoring pH and metabolic activity of living cells.

Quantitative detection of biological and chemical species is critical to numerous areas of medical and life sciences. In this context, information regarding pH is of central importance in multiple areas, from chemical analysis, through biomedical basic studies and medicine, to industry. Therefore, a continuous interest exists in developing new, rapid, miniature, biocompatible and highly sensitive pH sensors for minute fluid volumes. Here, we present a new paradigm in the development of optoelectrical sensing nanodevices with built-in self-calibrating capabilities. The proposed electrical devices, modified with a photoactive switchable molecular recognition layer, can be optically switched between two chemically different states, each having different chemical binding constants and as a consequence affecting the device surface potential at different extents, thus allowing the ratiometric internal calibration of the sensing event. At each point in time, the ratio of the electrical signals measured in the ground and excited states, respectively, allows for the absolute concentration measurement of the molecular species under interest, without the need for electrical calibration of individual devices. Furthermore, we applied these devices for the real-time monitoring of cellular metabolic activity, extra- and intracellularly, as a potential future tool for the performance of basic cell biology studies and high-throughput personalized medicine-oriented research, involving single cells and tissues. This new concept can be readily expanded to the sensing of additional chemical and biological species by the use of additional photoactive switchable receptors. Moreover, this newly demonstrated coupling between surface-confined photoactive molecular species and nanosensing devices could be utilized in the near future in the development of devices of higher complexity for both the simultaneous control and monitoring of chemical and biological processes with nanoscale resolution control.

Unwrapping core-shell nanowires into nanoribbon-based superstructures.

A prize for the ribbons: High-quality crystalline semiconducting nanoribbons can be prepared by "unwrapping" core-shell nanowire precursors. For example, Ge nanowires were coated with a Si shell and the top surface was carved by etching whereas the sides were protected by a thin layer of photoresist material. Finally the Ge core was removed selectively by chemical means to give fully opened and flat nanoribbon structures.