Real‐Time Probing of Nanowire Assembly Kinetics at the Air–Water Interface by In Situ Synchrotron X‐Ray Scattering

Although many assembly strategies have been used to successfully construct well‐aligned nanowire (NW) assemblies, the understanding of their assembly kinetics has remained elusive, which restricts the development of NW‐based device and circuit fabrication. Now a versatile strategy that combines interfacial assembly and synchrotron‐based grazing‐incidence small‐angle X‐ray scattering (GISAXS) is presented to track the assembly evolution of the NWs in real time. During the interface assembly process, the randomly dispersed NWs gradually aggregate to form small ordered NW‐blocks and finally are constructed into well‐defined NW monolayer driven by the conformation entropy. The NW assembly mechanism can be well revealed by the thermodynamic analysis and large‐scale molecular dynamics theoretical evaluation. These findings point to new opportunities for understanding NW assembly kinetics and manipulating NW assembled structures by bottom‐up strategy.     

Effects of ZnO nanowire length on surface-assisted laser desorption/ionization of small molecules

The effects of nanowire (NW) length on surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS) of small molecules were investigated using ZnO NWs of 50 nm diameter with a broad range of lengths ranging from 25 to 1600 nm. Characterization of the ZnO NWs revealed that the length was the only parameter that varied in this study, while other properties of the NWs remained essentially the same as the bulk properties. Experiments on SALDI efficiency exhibited that the SALDI processes on NWs have a certain length window. In the present case of ZnO NWs, the SALDI efficiency was found to be enhanced on the nanowires of 250 nm length, corresponding to an aspect ratio of 5. The roles of NW length in the SALDI processes were discussed from the viewpoint of efficient energy-transfer media as well as physical obstacles screening laser irradiation and preventing the escape of nascent ions from NW surfaces. The existence of the length window may provide valuable insight for tailoring new nanostructures for efficient SALDI of small molecules.     

Synthesis of single crystal Sn-doped In(2)O(3) nanowires: size-dependent conductive characteristics

Single crystalline Sn doped In(2)O(3) (ITO) NWs (nanowires) were synthesized via an Au-catalyzed VLS (vapor-liquid-solid) method at 600 °C. The different sizes (～20, ～40, ～80 nm) of the Au NPs (nanoparticles) provided the controllable diameters for ITO NWs during growth. Phase and microstructures confirmed by high-resolution transmission electron microscope images (HRTEM) and X-ray diffraction (XRD) spectra indicated that the phase of In(2)O(3) NWs had a growth direction of [100]. X-ray photoelectron spectroscopy (XPS) was employed to obtain the chemical compositions of the ITO NWs as well as the ratio of Sn/In and oxygen concentrations. The findings indicated that low resistivity was found for ITO NWs with smaller diameters due to higher concentrations of oxygen vacancies and less incorporation of Sn atoms inside the NWs. The resistivity of NWs increases with increasing diameter due to more Sn atoms being incorporated into the NW and their reduction of the amount of oxygen vacancies. Low resistivity NWs could be achieved again due to excess Sn atoms doped into the large diameter NWs. Therefore, by optimizing the well-controlled growth of the NW diameter and interface states, we are able to tune the electrical properties of Sn-doped ITO NWs.     

Design, synthesis, and characterization of novel nanowire structures for photovoltaics and intracellular probes

Semiconductor nanowires (NWs) represent a unique system for exploring phenomena at the nanoscale and are expected to play a critical role in future electronic, optoelectronic, and miniaturized biomedical devices. Modulation of the composition and geometry of nanostructures during growth could encode information or function, and realize novel applications beyond the conventional lithographical limits. This review focuses on the fundamental science aspects of the bottom-up paradigm, which are synthesis and physical property characterization of semiconductor NWs and NW heterostructures, as well as proof-of-concept device concept demonstrations, including solar energy conversion and intracellular probes. A new NW materials synthesis is discussed and, in particular, a new "nanotectonic" approach is introduced that provides iterative control over the NW nucleation and growth for constructing 2D kinked NW superstructures. The use of radial and axial p-type/intrinsic/n-type (p-i-n) silicon NW (Si-NW) building blocks for solar cells and nanoscale power source applications is then discussed. The critical benefits of such structures and recent results are described and critically analyzed, together with some of the diverse challenges and opportunities in the near future. Finally, results are presented on several new directions, which have recently been exploited in interfacing biological systems with NW devices.     

Tuning the electrical transport properties of n-type CdS nanowires via Ga doping and their nano-optoelectronic applications

Gallium-doped n-type CdS nanowires (NWs) were successfully synthesized via a thermal evaporation method. The conductivities of the CdS NWs were dramatically improved by nearly nine orders of magnitude after Ga doping, and could be further tuned over a wide range by adjusting the doping level. High-performance metal-insulator-semiconductor field-effect transistors (MISFETs) were constructed based on the single CdS : Ga NW with high-κ Si(3)N(4) dielectrics and top-gate geometries. In contrast to back-gate FETs, the MISFETs revealed a substantial improvement in device performance. Nano-light emitting diodes (nanoLEDs) were fabricated from the CdS : Ga NWs by using a n-NW/p(+)-Si substrate hybrid device structure. The nanoLEDs showed a bright yellow emission at a low forward bias. It is expected that the Ga-doped CdS NWs with controlled electrical transport properties will have important applications in nano-optoelectronic devices.     

Nanowire Chemical/Biological Sensors: Status and a Roadmap for the Future

Chemiresistive sensors are becoming increasingly important as they offer an inexpensive option to conventional analytical instrumentation, they can be readily integrated into electronic devices, and they have low power requirements. Nanowires (NWs) are a major theme in chemosensor development. High surface area, interwire junctions, and restricted conduction pathways give intrinsically high sensitivity and new mechanisms to transduce the binding or action of analytes. This Review details the status of NW chemosensors with selected examples from the literature. We begin by proposing a principle for understanding electrical transport and transduction mechanisms in NW sensors. Next, we offer the reader a review of device performance parameters. Then, we consider the different NW types followed by a summary of NW assembly and different device platform architectures. Subsequently, we discuss NW functionalization strategies. Finally, we propose future developments in NW sensing to address selectivity, sensor drift, sensitivity, response analysis, and emerging applications.     

Au Nanowire–Au Nanoparticles Conjugated System which Provides Micrometer Size Molecular Sensors

We report a new type of molecular sensor using a Au nanowire (NW)–Au nanoparticles (NPs) conjugated system. The Au NW–NPs structure is fabricated by the self‐assembly of biotinylated Au NPs on a biotinylated Au NW through avidin; this creates hot spots between NW and NPs that strongly enhance the Raman signal. The number of the Au NPs attached to the NW is reproducibly proportional to the concentration of the avidin, and is also proportional to the measured surface‐enhanced Raman scattering (SERS) signals. Since this well‐defined NW–NPs conjugated sensor is only a few micrometer long, we expect that development of multiplex nanobiosensor of a few tens micrometer size would become feasible by combining individually modified multiple Au NWs together on one substrate.     

Rapid Capillary-Assisted Solution Printing of Perovskite Nanowire Arrays Enables Scalable Production of Photodetectors

Despite recent progress in producing perovskite nanowires (NWs) for optoelectronics, it remains challenging to solution-print an array of NWs with precisely controlled position and orientation. Herein, we report a robust capillary-assisted solution printing (CASP) strategy to rapidly access aligned and highly crystalline perovskite NW arrays. The key to the CASP approach lies in the integration of capillary-directed assembly through periodic nanochannels and solution printing through the programmably moving substrate to rapidly guide the deposition of perovskite NWs. The growth kinetics of perovskite NWs was closely examined by in situ optical microscopy. Intriguingly, the as-printed perovskite NWs array exhibit excellent optical and optoelectronic properties and can be conveniently implemented for the scalable fabrication of photodetectors.     

Rapid Capillary‐Assisted Solution Printing of Perovskite Nanowire Arrays Enables Scalable Production of Photodetectors

Despite recent progress in producing perovskite nanowires (NWs) for optoelectronics, it remains challenging to solution‐print an array of NWs with precisely controlled position and orientation. Herein, we report a robust capillary‐assisted solution printing (CASP) strategy to rapidly access aligned and highly crystalline perovskite NW arrays. The key to the CASP approach lies in the integration of capillary‐directed assembly through periodic nanochannels and solution printing through the programmably moving substrate to rapidly guide the deposition of perovskite NWs. The growth kinetics of perovskite NWs was closely examined by in situ optical microscopy. Intriguingly, the as‐printed perovskite NWs array exhibit excellent optical and optoelectronic properties and can be conveniently implemented for the scalable fabrication of photodetectors.     

Selective functionalization of In2O3 nanowire mat devices for biosensing applications

A strategy to covalently attach biological molecules to the electrochemically active surface of indium oxide nanowire (In2O3 NW) mat devices is presented. A self-assembled monolayer (SAM) of 4-(1,4-dihydroxybenzene)butyl phosphonic acid (HQ-PA) was generated on an indium tin oxide (ITO)-coated glass and In2O3 NWs surface. The chemical steps required for surface derivatization were optimized on an ITO surface prior to modifying the In2O3 NWs. The hydroquinone group contained in the HQ-PA SAM was electrochemically oxidized to quinone (Q-PA) at +330 mV. The monolayer of Q-PA was allowed to react with a thiol-terminated DNA. The DNA was paired to its complementary strand tagged with a fluorescence dye. Attachment of DNA was verified using fluorescence microscopy. A device was subsequently prepared on a SiO2-supported mat of In2O3 NWs by depositing gold electrodes on the mat surface. The reaction strategy optimized on ITO was applied to this In2O3 NW-based device. Arrays of In2O3 NWs on a single substrate were electrochemically activated in a selective manner to Q-PA. Activated In2O3 NWs underwent reaction with HS-DNA and gave a positive fluorescence response after pairing with the dye-DNA. The unactivated In2O3 NWs gave no response, thus demonstrating selective functionalization of an In2O3 NW array. This can be considered a key step for the future fabrication of large-scale, inexpensive, nanoscale biosensors.     

Early stages of oxide growth in H-terminated silicon nanowires: determination of kinetic behavior and activation energy

Silicon nanowires (Si NWs) terminated with hydrogen atoms exhibit higher activation energy under ambient conditions than equivalent planar Si(100). The kinetics of sub-oxide formation in hydrogen-terminated Si NWs derived from the complementary XPS surface analysis attribute this difference to the Si-Si backbond and Si-H bond propagation which controls the process at lower temperatures (T < 200 °C). At high temperatures (T≥ 200 °C), the activation energy was similar due to self-retarded oxidation. This finding offers the understanding of early-stage oxide growth that affects the conductance of the near-gap channels leading towards more efficient Si NW electronic devices.     

"Lens" effect in directed assembly of nanowires on gradient molecular patterns

We report a new phenomenon, named here as the "lens" effect, in the directed-assembly process of nanowires (NWs) on self-assembled monolayer (SAM) patterns. In this process, the adsorption of NWs is focused in the nanoscale regions at the center of microscale SAM patterns with gradient surface molecular density just like an optical lens focuses light. As a proof of concepts, we successfully demonstrated the massive assembly of V2O5 NWs and single-walled carbon nanotubes (swCNTs) with a nanoscale resolution using only microscale molecular patterning methods. This work provides us with important insights about the directed-assembly process, and from a practical point of view, it allows us to generate nanoscale patterns of NWs over a large area for mass fabrication of NW-based devices.     

Organic‐Stabilizer‐Free Polyol Synthesis of Silver Nanowires for Electrode Applications

The polyol reduction of a Ag precursor in the presence of an organic stabilizer, such as poly(vinylpyrrolidone), is a widely used method for the production of Ag nanowires (NWs). However, organic capping molecules introduce insulating layers around each NW. Herein we demonstrate that Ag NWs can be produced in high yield without any organic stabilizers simply by introducing trace amounts of NaCl and Fe(NO₃)₃ during low‐temperature polyol synthesis. The heterogeneous nucleation and growth of Ag NWs on initially formed AgCl particles, combined with oxidative etching of unwanted Ag nanoparticles, resulted in the selective formation of long NWs with an average length of about 40 μm in the absence of a capping or stabilizing effect provided by surface‐adsorbing molecules. These organic‐stabilizer‐free Ag NWs were directly used for the fabrication of high‐performance transparent or stretchable electrodes without a complicated process for the removal of capping molecules from the NW surface.     

Spontaneous self-organization enables dielectrophoresis of small nanoparticles and formation of photoconductive microbridges

Detailed understanding of the mechanism of dielectrophoresis (DEP) and the drastic improvement of its efficiency for small size-quantized nanoparticles (NPs) open the door for the convergence of microscale and nanoscale technologies. It is hindered, however, by the severe reduction of DEP force in particles with volumes below a few hundred cubic nanometers. We report here DEP assembly of size-quantized CdTe nanoparticles (NPs) with a diameter of 4.2 nm under AC voltage of 4-10 V. Calculations of the nominal DEP force for these NPs indicate that it is several orders of magnitude smaller than the force of the Brownian motion destroying the assemblies even for the maximum applied AC voltage. Despite this, very efficient formation of NP bridges between electrodes separated by a gap of 2 μm was observed even for AC voltages of 6 V and highly diluted NP dispersions. The resolution of this conundrum was found in the intrinsic ability of CdTe NPs to self-assemble. The species being assembled by DEP are substantially bigger than the individual NPs. DEP assembly should be treated as a process taking place for NP chains with a length of ~140 nm. The self-assembled chains increase the nominal volume where the polarization of the particles takes place, while retaining the size-quantized nature of the material. The produced NP bridges were found to be photoactive, producing photocurrent upon illumination. DEP bridges of quantum confined NPs can be used in fast parallel manufacturing of novel MEMS components, sensors, and optical and optoelectronic devices. Purposeful engineering of self-assembling properties of NPs makes possible further facilitation of the DEP and increase of complexity of the produced nano- and microscale structures.     

Solution-based growth and structural characterization of homo- and heterobranched semiconductor nanowires

Colloidal homobranched ZnSe nanowires (NWs) and heterobranched CdSe-ZnSe NWs are successfully synthesized by combining a sequential seeding strategy with the solution-liquid-solid (SLS) growth process. We have developed an efficient approach to deposit secondary bismuth nanoparticles onto the NW backbone to induce the subsequent SLS branch growth. The density, length, and diameter of branches are rationally controlled by varying reaction conditions. Structural characterization reveals that crystalline branches grow epitaxially from the backbone in both homo- and heterobranched NWs. Two different branching structures are observed in the CdSe-ZnSe heterobranched NWs, owing to the phase admixture, i.e., cubic and hexagonal crystal structures, coexisting in the CdSe NW backbones. These branched NWs with well-designed architectures are expected to have potential as three-dimensional building blocks in the fabrication of nanoscale electronics and photonics.     

Dielectrophoresis and AC-induced assembly in binary colloidal suspensions

Dielectrophoretic behaviors and assembly of a binary suspension in aqueous media are examined in the presence of nonuniform alternating current (AC) electric field. A peculiar low-frequency threshold and dielectrophoresis (DEP) crossover frequency determine the applicable frequency window for binary assembly under positive DEP, which can be effectively tuned by medium conductivity and particle size, suggesting that the dynamic double-layer effect is responsible for the interfacial polarization of micrometer to submicrometer-sized particles in aqueous suspensions. Strong effects of AC-field frequency, medium conductivity, and size ratio on binary assembly morphology have been observed. A frequency-medium conductivity phase diagram is obtained to illustrate the morphological transition of assembled colloidal aggregates from segregated, ordered assemblies to inverted segregation with the appearance of amorphous phases upon increasing frequency and/or medium conductivity, which is a direct consequence of the competition between DEP and hydrodynamic mobility. Significantly, our results demonstrate a rapid method to form hybrid nanostructured materials.     

Surfactant-free, large-scale, solution-liquid-solid growth of gallium phosphide nanowires and their use for visible-light-driven hydrogen production from water reduction

Colloidal GaP nanowires (NWs) were synthesized on a large scale by a surfactant-free, self-seeded solution-liquid-solid (SLS) method using triethylgallium and tris(trimethylsilyl)phosphine as precursors and a noncoordinating squalane solvent. Ga nanoscale droplets were generated in situ by thermal decomposition of the Ga precursor and subsequently promoted the NW growth. The GaP NWs were not intentionally doped and showed a positive open-circuit photovoltage based on photoelectrochemical measurements. Purified GaP NWs were used for visible-light-driven water splitting. Upon photodeposition of Pt nanoparticles on the wire surfaces, significantly enhanced hydrogen production was observed. The results indicate that colloidal surfactant-free GaP NWs combined with potent surface electrocatalysts could serve as promising photocathodes for artificial photosynthesis.     

Hybrid Platforms of Silicon Nanowires and Carbon Nanotubes in an Ionic Liquid Bucky Gel

Silicon nanowires (NWs) are appealing building blocks for low-cost novel concept devices with improved performances. In this research paper, we realized a hybrid platform combining an array of vertically oriented Si NWs with different types of bucky gels, obtained from carbon nanotubes (CNT) dispersed into an ionic liquid (IL) matrix. Three types of CNT bucky gels were obtained from imidazolium-based ionic liquids (BMIM-I, BIMI-BF₄, and BMIM-Tf₂N) and semiconductive CNTs, whose structural and optical responses to the hybrid platforms were analyzed and compared. We investigated the electrical response of the IL-CNT/NW hybrid junctions in dark and under illumination for each platform and its correlation to the ionic liquid characteristics and charge mobility. The reported results confirm the attractiveness of such IL-CNT/NW hybrid platforms as novel light-responsive materials for photovoltaic applications. In particular, our best performing cell reported a short-circuit current density of 5.6 mA/cm² and an open-circuit voltage of 0.53 V.     

An All‐Inorganic Colloidal Nanocrystal Flexible Polarizer

Inorganic single crystals with anisotropic structures usually suffer from high brittleness and stiffness. Flexible polymers are used to replace inorganic crystals, but the hot‐stretching‐induced orientation process is tedious, and oriented molecular chains tend to revert to random coils during aging. To overcome these obstacles and using the similarities between sub‐1 nm nanowires (NWs) and linear polymers, we successfully fabricated anisotropic, transparent, flexible, and stable (ATFS) NW films with great potential for optical applications through a wet‐spinning method. The NW films show birefringence, and their birefractive index is higher than that of many polymers. They also showed polarized absorption of UV light and anisotropic scattering of visible light. The integrated films composed of NWs and quantum dots showed good fluorescence polarization. The tedious synthesis of quantum rods and fabrication of oriented polymer films can thus be avoided.     

Stereoaligned Epitaxial Growth of Single‐Crystalline Platinum Nanowires by Chemical Vapor Transport

Epitaxial Pt nanowire (NW) arrays are synthesized for the first time by a chemical vapor transport method by using a metal halide as a precursor. Here we report that the epitaxial growth direction of NWs can be steered by seed crystal morphology. Octahedral seeds grow into inclined NWs possessing six growth directions, whereas half‐octahedral seeds grow into vertical and horizontal NWs. Interfacial energies between the seed material and the substrate are critical in determining the morphology of seed crystals. We also demonstrate that non‐SERS‐active Pt NWs can show strong surface‐enhanced Raman scattering (SERS) spectra by placing them on Ag films. The active SERS observation would help to elucidate platinum‐catalyzed chemical reactions.