Micro-“factory” for self-assembled peptide nanostructures

This study describes an integrated micro “factory” for the preparation of biological self-assembled peptide nanotubes and nanoparticles on a polymer chip, yielding controlled growth conditions. Self-assembled peptides constitute attractive building blocks for the fabrication of biological nanostructures due to the mild conditions of their synthesis process. This biological material can form nanostructures in a rapid way and the synthesis method is less expensive as compared to that of carbon nanotubes or silicon nanowires. The present article thus reports on the on-chip fabrication of self-assembled peptide nanostructures by means of a microfluidic device that is able to resist the harsh conditions imposed by the solvent used during the nanostructure synthesis. This on-chip fabrication was found to be simple, rapid, and convenient.     

Efficient flexible organic photovoltaics using silver nanowires and polymer based transparent electrodes

Planarization and filling voids between wires are key issues when using nanowire electrodes in flexible solar cells such as organic photovoltaics (OPV). For this purpose, we use poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) which leads to an electrically well connected silver nanowire (AgNW) network. Furthermore, the use of water based PEDOT: PSS leads to humidity assisted AgNW fusing, resulting in a maximum processing temperature of only 120 °C. OPV cells using this AgNW/PEDOT: PSS transparent electrodes exhibit power conversion efficiencies up to 7.15%. Moreover, OPV devices on PET substrates with an alumina encapsulation and barrier adhesive show excellent mechanical flexibility.     

Structural and optical properties of silicon nanowires synthesized by Ag-assisted chemical etching

Metal-assisted chemical etching (MACE) of silicon in an aqueous solution of hydrofluoric acid and hydrogen peroxide is established for the fabrication of large-area uniform silicon nanowire (SiNW) arrays. The effect of the silver catalyst layer thickness on the morphology of the synthesized nanostructures and nanowires is investigated. Atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM) reveal that the morphology of the fabricated silicon nanostructures remarkably depends on the catalyst layer thickness, and an optimum layer thickness is necessary for the fabrication of SiNWs. Also the effect of different etching times on the structural and optical properties of the fabricated SiNWs is investigated. FESEM showed a linear increment of the nanowire length and slight diameter changes through different etching times. The ultralow reflectance of SiNWs in the absorption region through the measurement of specular and diffuse reflectance showed that with increase in the etching time, the total reflectance remarkably decreases. A broadband visible photoluminescence (PL) emission from these wires was observed, and it could be stated that the silicon nanocrystals (SiNCs) are mostly responsible for the PL emission. The SiNC sizes were determined by an analytical model through a frequency shift in the Raman spectrum. The synthesized optically-active SiNWs could, therefore, be considered as a promising candidate for a new generation of nanoscale opto-electronic devices.     

Top down fabrication of long silicon nanowire devices by means of lateral oxidation

The process for the fabrication of devices based on a single silicon nanowire with a triangular section is presented and discussed. The top down fabrication process exploits the properties of silicon anisotropic etching for the realization of very regular trapezoidal structures, that can be uniformly reduced in controlled way by means of lateral oxidation. This allows the reproducible realization of nanowires smaller than 20 nm, and with a length of several micrometers, starting from relatively big structures that, even if electron beam lithography has been used in the present work, could be realized also by other (as optical) lithographic techniques. Nanowires are already placed between silicon contacts for electrical transport characterization. The process, compatible with the actual MOS technology, is suitable for a massive, large-scale production of silicon nanowire based devices and it allows a flexible platform for multigate and more complex structures and devices. The nanowire triangular section is a step toward the integration of three-dimensional devices. Electrical characteristics of silicon nanowire FETs, both p- and n-doped, will be reported and discussed.     

Solution processable PEDOT:PSS based hybrid electrodes for organic field effect transistors

We report high performance solution processed conductive inks used as contact electrodes for printed organic field effect transistors (OFETs). Poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) electrodes show highly improved very low sheet resistance of 65.8 ± 6.5 Ω/square (Ω/□) by addition of dimethyl sulfoxide (DMSO) and post treatment with methanol (MeOH) solvent. Sheet resistance was further improved to 33.8 ± 8.6 Ω/□ by blending silver nanowire (AgNW) with DMSO doped PEDOT:PSS. Printed OFETs with state of the art diketopyrrolopyrrole-thieno[3,2-b]thiophene (DPPT-TT) semiconducting polymer were demonstrated with various solution processable conductive inks, including bare, MeOH treated PEDOT:PSS, single wall carbon nanotubes, and hybrid PEDOT:PSS-AgNW, as the source and drain (S/D) electrode by spray printing using a metal shadow mask. The highest field effect mobility, 0.49 ± 0.03 cm² V⁻¹ s⁻¹ for DPPT-TT OFETs, was obtained using blended AgNW with DMSO doped PEDOT:PSS S/D electrode.     

Neutral-pH PEDOT:PSS as over-coating layer for stable silver nanowire flexible transparent conductive films

The silver nanowire (AgNW) mesh film with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the over-coating layer is a promising flexible transparent conductive film technology. In this work, experimental studies show that the hygroscopic and acid properties of the common PEDOT:PSS lead to poor stabilities of the composite films, due to the conductivity degradation of PEDOT:PSS by the water absorption and the acid corrosion of AgNWs by PEDOT:PSS. By using the modified PEDOT:PSS of neutral pH as the over-coating layer, the long term shelf-life time, thermal and current stressing stabilities are all significantly improved without sacrifice of transparency, electrical conductivity and mechanical flexibility. Under both cases of thermal aging test at 210 °C for 20 min and 12 h continuous current stressing at a current density of 30 mA/cm², no obvious change of the conductivity is observed. The results clearly demonstrate that using the neutral-pH PEDOT:PSS as an over-coating layer can help to achieve flexible AgNW transparent conductive films with superior stability for flexible optoelectronic devices.     

The enhancement of electrical and optical properties of PEDOT:PSS using one-step dynamic etching for flexible application

The conductivity enhancement of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) by dynamic etching process was investigated to introduce the outstanding and simplest method for soft electronics. Four different samples which were pristine PEDOT:PSS, PEDOT:PSS doped with 5 wt.% DMSO, PEDOT:PSS with dipping process, and PEDOT:PSS with dynamic etching process were prepared to compare the properties such as conductivity, morphology, relative atomic percentage, and topography. All samples were characterized by four point probe, current atomic force microscopy (C-AFM), X-ray photoelectron spectroscopy (XPS), and UV–visible spectroscopy. The conductivity of the sample with dynamic etching process showed the highest value as 1299 S/cm among four samples. We proved that the dynamic etching process is superior to remove PSS phase from PEDOT:PSS film, to flow strong current through entire surface of PEDOT:PSS, and to show the smoothest surface (RMS 2.28 nm). XPS analysis was conducted for accurate chemical and structural surface environments of four samples and the relative atomic percentage of PEDOT in the sample with dynamic etching was the highest as 29.5%. The device performance of the sample with the dynamic etching process was outstanding as 10.31 mA/cm² of J_sc, 0.75 eV of V_oc, 0.46 of FF, and 3.53% of PCE. All properties and the device performance for PEDOT:PSS film by dynamic etching process were the most excellent among the samples.     

Formation of Nickel Oxide Nanotubes with Uniform Wall Thickness by Low‐Temperature Thermal Oxidation Through Understanding the Limiting Effect of Vacancy Diffusion and the Kirkendall Phenomenon

In this work, the step‐wise oxidation mechanism of nickel (Ni) nanowires is elucidated. Rapid vacancy diffusion plays a significant role at low temperatures in forming heterostructures of nickel oxide (NiO) nanotubes with Ni nanowires. Subsequent investigations of Ni nanowire oxidation at higher temperatures and faster temperature ramp rates show that it is difficult to bypass this rapid vacancy diffusion stage, which affects the formation of the final structure. Therefore, it is unlikely to form solid NiO nanowires or NiO nanotubes with uniform wall thickness through the conventional annealing/oxidation process of Ni nanowires. Instead, a step‐wise oxidation process by combining low temperature oxidation with a chemical etching step is utilized to produce for the first time NiO nanotubes with uniform wall thickness from Ni nanowires.     

Formation of 1D Poly(3,4‐ethylenedioxythiophene) Nanomaterials in Reverse Microemulsions and Their Application to Chemical Sensors

1D poly(3,4‐ethylenedioxythiophene) (PEDOT) nanomaterials, including ellipsoidal nanoparticles, nanorods, and nanotubes, are fabricated via chemical oxidation polymerization in reverse (water‐in‐oil) microemulsions. The reverse cylindrical micelles are prepared with sodium bis(2‐ethylhexyl) sulfosuccinate (AOT) and aqueous FeCl₃ solution in hexane. The morphology of the final products is determined by carefully tuning the degree of oxidation potential at the micelle surface. Notably, the fabrication of gram‐scale amounts of products is possible under optimized synthetic conditions, suggesting that this methodology is appropriate for the large‐scale production of the corresponding nanomaterials. The as‐prepared PEDOT nanomaterials are applied to the precise detection of alcohol vapors. The chemical sensors based on the PEDOT nanomaterials present excellent reversibility and reproducibility in response.     

Hybrid LEDs based on ZnO nanowire structures

This paper summarized the research, development, and state of the art of hybrid ZnO nanowire LEDs, in which electroluminescence is generated at the junction between n-type doped ZnO nanowire structures and specific p-type doped polymers (in particular PEDOT, PEDOT:PSS, or PFO). Different device architectures will be reviewed and discussed with a particular emphasis on the electronic transport through the hybrid structures and the microscopic processes of light emission. Finally, a gas-phase deposition technique for conductive polymers will be presented which might help improve the performance of hybrid ZnO nanowire LEDs in the future.     

Universal Platform for Scalable Semiconductor-Superconductor Nanowire Networks

Semiconductor-superconductor hybrids are commonly used in research on topological quantum computation. Traditionally, top-down approaches involving dry or wet etching are used to define the device geometry. These often aggressive processes risk causing damage to material surfaces, giving rise to scattering sites particularly problematic for quantum applications. Here, a method that maintains the flexibility and scalability of selective area grown nanowire networks while omitting the necessity of etching to create hybrid segments is proposed. Instead, it takes advantage of directional growth methods and uses bottom-up grown indium phosphide (InP) structures as shadowing objects to obtain selective metal deposition. The ability to lithographically define the position and area of these objects and to grow a predefined height ensures precise control of the shadowed region. The approach by growing indium antimonide nanowire networks with well-defined aluminium and lead (Pb) islands is demonstrated. Cross-section cuts of the nanowires reveal a sharp, oxide-free interface between semiconductor and superconductor. By growing InP structures on both sides of in-plane nanowires, a combination of platinum and Pb can independently be shadow deposited, enabling a scalable and reproducible in situ device fabrication. The semiconductor-superconductor nanostructures resulting from this approach are at the forefront of material development for Majorana based experiments.     

Genetically Modifiable Flagella as Templates for Silica Fibers: From Hybrid Nanotubes to 1D Periodic Nanohole Arrays

Bacterial flagellum is a protein nanotube that is helically self‐assembled from thousands of a protein subunit called flagellin. The solvent‐exposed domain of each flagellin on the flagella is genetically modifiable, in that a foreign peptide can be genetically inserted into this domain, leading to the high‐density display of this foreign peptide on the surface of flagella. In this work, wild‐type and genetically engineered flagella (inner diameter of ～2 nm and outer diameter of ～14 nm) detached from the surface of Salmonella bacterial cells are used as templates to site‐specifically form silica sheaths on the flagellar surface, resulting in the formation of double‐layered silica/flagella nanotubes. The flagella templates inside the silica/flagella nanotubes can be removed to obtain silica nanotubes by calcining the nanotubes at high temperature (550°C). Further calcination of the silica nanotubes at a higher temperature (800 °C) leads to the formation of a periodic nanohole array along the silica fibers with a center‐to‐center nanohole spacing of ～79 nm. It is demonstrated that the double‐layered silica‐flagella nanotubes can be used for selective CdTe quantum dot uptake into the inner channels or selective Au nanoparticle coating on the outer wall of the nanotubes due to the different chemistry between inner flagellum core (protein) and outer silica wall of the nanotubes. It is also found that flagella displaying different peptides result in different morphologies of the silica nanotubes. This work suggests that the monodisperse diameter and genetically tunable surface chemistry of the flagella can be exploited for the fabrication of silica nanotubes with uniform diameter and controllable morphologies as well as silica nanofibers decorated with periodic nanohole arrays.     

Silver nanowire/polymer composite soft conductive film fabricated by large-area compatible coating for flexible pressure sensor array

Soft conductive films composed of a silver nanowire (AgNW) network,a neutral-pH PEDOT:PSS overcoating layer and a polydimethylsiloxane (PDMS) elastomer substrate are fabricated by large area compatible coating processes.The neutral-pH PEDOT:PSS layer is shown to be able to significantly improve the conductivity,stretchability and air stability of the conductive films.The soft conductive films are patterned using a simple maskless patterning approach to fabricate an 8 × 8 flexible pressure sensor array.It is shown that such soft conductive films can help to improve the sensitivity and reduce the signal crosstalk over the pressure sensor array.     

Organic low voltage rewritable memory device based on PEDOT:PSS/f-MWCNTs thin film

We report on devices constructed using a small quantity (?0.01 wt.%) of functionalized multiwalled carbon nanotubes (f-MWCNTs) embedded in a conducting polymer (poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), PEDOT:PSS) matrix and aluminum top electrodes, prepared on indium-tin-oxide (ITO) substrates. Our ITO/(PEDOT:PSS + f-MWCNTs)/Al devices show current bistability. The low resistance ON-state, as well as the high resistance OFF state, retain the information for hours and are stable after hundreds of write–read–erase–read (WRER) cycles, being potentially interesting for erasable and rewritable volatile memory device applications. Moreover, the operation voltages used for performing these WRER cycles are very low. The threshold voltage for OFF to ON switching can be adjusted changing the f-MWCNTs concentration. Our results suggest that the nanotubes are necessary for the production of an inhomogeneous electric field playing a role in the electroforming (dielectric breakdown) of the aluminum oxide layer at the Al₂O₃/(PEDOT:PSS) interface.     

Ultrasmooth,highly conductive and transparent PEDOT:PSS/silver nanowire composite electrode for flexible organic light-emitting devices

The next generation of optoelectronic devices requires transparent conductive electrodes to be flexible, inexpensive and compatible with large scale manufacturing processes. We report an ultrasmooth, highly conductive and transparent composite electrode on a flexible photopolymer substrate by employing a template stripping method. A random silver nanowire (AgNW) network buried in poly(3,4ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film constituted the composite electrode. Besides the effectively decreased surface roughness, its sheet resistance and transmittance are comparable to those of conventional PEDOT:PSS electrode. As a result, the efficiency of the OLEDs based on the composite electrode exhibited 25% enhancement compared to the OLEDs with conventional PEDOT:PSS electrode. Moreover, the performance of the flexible OLEDs remains stable after over one hundred bending cycles.     

A comparative assessment of surface microstructure and electrical conductivity dependence on co-solvent addition in spin coated and inkjet printed poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT:PSS)

This study focuses on the fabrication of poly(3,4-ethylenedioxythiophene):polystyrene sulphonate (PEDOT:PSS) thin films by inkjet printing and investigates the developed surface morphology and electrical conductivity of the printed films as a function of the concentration of dimethyl sulfoxide (DMSO), added as conduction enhancing co-solvent, and Surfynol, added as a surfactant. The printed films are compared with PEDOT:PSS films fabricated by the traditional spin coating technique. Measurements of the surface tension justify including surfactant as a processing additive, where addition of 1% Surfynol results in substantial decrease of the surface tension of the PEDOT:PSS solution, whilst it also increases film surface roughness by an order of magnitude for both fabrication methods. The addition of 5 wt% DMSO is shown to result in a 10³ decrease in sheet resistance for both spin coated and inkjet printed films with both processing routes demonstrating decrease in surface roughness and coarsening of PEDOT grains as a function of the co-solvent concentration, whilst X-ray photon spectroscopy showed an increase in the surface PEDOT to PSS ratio from 0.4 to 0.5. Inkjet printed films have lower sheet resistance than the corresponding spin coated films, whilst atomic force microscopy reveals a coarser surface morphology for the inkjet printed films. The findings in this work point out at the decrease of sheet resistance due to coarsening of PEDOT grains which is linked to a decrease of surface roughness for small RMS values associated with the PEDOT grains. However, the higher surface roughness generated when Surfynol surfactant was added was not detrimental to the film’s in-plane conductivity due to the fact that these higher roughness values were unrelated to the PEDOT grains.     

Direct Water‐Writing/Electroerasing Pattern on PEDOT Inverse Opals

This work presents a reversible direct water‐writing/electroerasing pattern on poly(3,4‐ethylene dioxythiophene) inverse opals (PEDOT‐IOs). The PEDOT‐IO‐0 is fabricated by potentiostatic polymerization of EDOT such that PEDOT infiltrates the interstices of a photonic crystal (PC) template, and the template is subsequently removed. The PEDOT‐IO‐I is obtained by reducing PEDOT‐IO‐0. There are four states and three different switches of PEDOT‐IOs: the first switch is the irreversible reduction of PEDOT‐IO‐0 to PEDOT‐IO‐I (neutral state). The second switch is the reversible electrochemical process between neutral and oxidized PEDOT‐IO‐I accompanied by a reversible stopband shift owing to ionic doping/dedoping. The third switch is the water treatment process of PEDOT‐IO‐I (oxidation state) to form PEDOT‐IO‐II, which induces a blueshift in the stopband owing to water‐induced removal of ions and shrinkage of the periodic structure. Combining the switches of PEDOT‐IO‐I and PEDOT‐IO‐II, a reversible water‐writing/electroerasing procedure is realized in the full‐solid state, producing multicolor patterns by water (a friendly ink) writing at different times. The as‐prepared PC pattern could be erased electrochemically. Reversible e‐paper can be successfully achieved based on the switches of PEDOT‐IOs, providing a novel method for the fabrication of functional optic materials.     

Soft Imprinting: Creating Highly Ordered Porous Anodic Alumina Templates on Substrates for Nanofabrication

We demonstrate a “soft‐imprinting” method for the fabrication of highly ordered porous anodic alumina (HOPAA) templates on different substrates (such as Si, glass slides, and flexible polyimide films) over large areas (> 1.5 cm²). In this process, Ar plasma etching is employed to soft imprint an evaporated Al film on the substrates using a free‐standing HOPAA template as a mask, thus creating ordered nanoindentations on the Al surface. The ordered nanoindentations in turn guide the subsequent anodization of Al to generate HOPAA templates on the substrates (HOPAA–substrates), which inherit the pattern of the free‐standing HOPAA mask. This soft‐imprinting technique is also applicable to the fabrication of HOPAA on flexible polymer films. To demonstrate the potential uses of the HOPAA–substrates in nanofabrication, highly ordered Au nanowire arrays are fabricated on a Si substrate and TiO₂ nanotube arrays are prepared on a glass substrate via solution‐ and vapor‐based fabrication processes, respectively.     

纳米线、纳米管的制备、表征及其应用

在高度集成化浪潮的推动下,现代技术对纳米尺度功能器件的需求将越来越迫切。纳米线、纳米管等一维材料作为纳米器件中必不可少的功能组件,在纳米研究领域中的地位显得愈发重要。本文从一维纳米材料的研究范畴入手,介绍了纳米线、纳米管的制备方法,技术要点以及各种相关表征方法,并涉及了当前一维纳米材料的一些应用研究,为基于纳米线、纳米管功能器件的研制提供前期参考。     

Metal‐Catalyzed Etching of Vertically Aligned Polysilicon and Amorphous Silicon Nanowire Arrays by Etching Direction Confinement

A systematic study of metal‐catalyzed etching of (100), (110), and (111) silicon substrates using gold catalysts with three varying geometrical characteristics: isolated nanoparticles, metal meshes with small hole spacings, and metal meshes with large hole spacings is carried out. It is shown that for both isolated metal catalyst nanoparticles and meshes with small hole spacings, etching proceeds in the crystallographically preferred <100> direction. However, the etching is confined to the single direction normal to the substrate surface when a catalyst meshes with large hole spacings is used. We have also demonstrated that the metal catalyzed etching method when used with metal mesh with large hole spacings can be extended to create arrays of polycrystalline and amorphous vertically aligned silicon nanowire by confining the etching to proceed in the normal direction to the substrate surface. The ability to pattern wires from polycrystalline and amorphous silicon thin films opens the possibility of making silicon nanowire array‐based devices on a much wider range of substrates.