Graphene: nanoscale processing and recent applications

One of the most interesting features of graphene is the rich physics set up by the various nanostructures it may adopt. The planar structure of graphene makes this material ideal for patterning at the nanoscale. The breathtakingly fast evolution of research on graphene growth and preparation methods has made possible the preparation of samples with arbitrary sizes. Available sample production techniques, combined with the right patterning tools, can be used to tailor the graphene sheet into functional nanostructures, even whole electronic circuits. This paper is a review of the existing graphene patterning techniques and potential applications of related lithographic methods.     

The interplay of structural and optical properties in individual ZnO nanostructures

Semiconductor nanostructures exhibit unique properties distinct from their bulk counterparts by virtue of nanoscale dimensions; in particular, exceptionally large surface area-to-volume ratios relative to that of the bulk produce variations in surface state populations that have numerous consequences on materials properties. Of the low-dimensional semiconductor nanostructures, nanowires offer a unique prospect in nanoscale optoelectronics due to their one-dimensional architecture. Already, many devices based upon individual nanowires have been demonstrated, but questions about how nano-size and structural variations affect the underlying materials properties still remain unanswered. Here, we focus on understanding the growth mechanism and kinetics of ZnO nanowires and related nanowalls, and their effects on nanoscale structural and optical properties.     

Aggregate nanostructures of organic molecular materials

Conjugated organic molecules are interesting materials because of their structures and their electronic, electrical, magnetic, optical, biological, and chemical properties. However, researchers continue to face great challenges in the construction of well-defined organic compounds that aggregate into larger molecular materials such as nanowires, tubes, rods, particles, walls, films, and other structural arrays. Such nanoscale materials could serve as direct device components. In this Account, we describe our recent progress in the construction of nanostructures formed through the aggregation of organic conjugated molecules and in the investigation of the optical, electrical, and electronic properties that depend on the size or morphology of these nanostructures. We have designed and synthesized functional conjugated organic molecules with structural features that favor assembly into aggregate nanostructures via weak intermolecular interactions. These large-area ordered molecular aggregate nanostructures are based on a variety of simpler structures such as fullerenes, perylenes, anthracenes, porphyrins, polydiacetylenes, and their derivatives. We have developed new methods to construct these larger structures including organic vapor-solid phase reaction, natural growth, association via self-polymerization and self-organization, and a combination of self-assembly and electrochemical growth. These methods are both facile and reliable, allowing us to produce ordered and aligned aggregate nanostructures, such as large-area arrays of nanowires, nanorods, and nanotubes. In addition, we can synthesize nanoscale materials with controlled properties. Large-area ordered aggregate nanostructures exhibit interesting electrical, optical, and optoelectronic properties. We also describe the preparation of large-area aggregate nanostructures of charge transfer (CT) complexes using an organic solid-phase reaction technique. By this process, we can finely control the morphologies and sizes of the organic nanostructures on wires, tubes, and rods. Through field emission studies, we demonstrate that the films made from arrays of CT complexes are a new kind of cathode materials, and we systematically investigate the effects of size and morphology on electrical properties. Low-dimension organic/inorganic hybrid nanostructures can be used to produce new classes of organic/inorganic solid materials with properties that are not observed in either the individual nanosize components or the larger bulk materials. We developed the combined self-assembly and templating technique to construct various nanostructured arrays of organic and inorganic semiconductors. The combination of hybrid aggregate nanostructures displays distinct optical and electrical properties compared with their individual components. Such hybrid structures show promise for applications in electronics, optics, photovoltaic cells, and biology. In this Account, we aim to provide an intuition for understanding the structure-function relationships in organic molecular materials. Such principles could lead to new design concepts for the development of new nonhazardous, high-performance molecular materials on aggregate nanostructures.     

Langmuir-Blodgettry of nanocrystals and nanowires

Although nanocrystals and nanowires have proliferated new scientific avenues in the study of their physics and chemistries, the bottom-up assembly of these small-scale building blocks remains a formidable challenge for device fabrication and processing. An attractive nanoscale assembly strategy should be cheap, fast, defect tolerant, compatible with a variety of materials, and parallel in nature, ideally utilizing the self-assembly to generate the core of a device, such as a memory chip or optical display. Langmuir-Blodgett (LB) assembly is a good candidate for arranging vast numbers of nanostructures on solid surfaces. In the LB technique, uniaxial compression of a nanocrystal or nanowire monolayer floating on an aqueous subphase causes the nanostructures to assemble and pack over a large area. The ordered monolayer can then be transferred to a solid surface en masse and with fidelity. In this Account, we present the Langmuir-Blodgett technique as a low-cost method for the massively parallel, controlled organization of nanostructures. The isothermal compression of fluid-supported nanoparticles or nanowires is unique in its ability to achieve control over nanoscale assembly by tuning a macroscopic property such as surface pressure. Under optimized conditions (e.g., surface pressure, substrate hydrophobicity, and pulling speed), it allows continuous variation of particle density, spacing, and even arrangement. For practical application and device fabrication, LB compression is ideal for forming highly dense assemblies of nanowires and nanocrystals over unprecedented surface areas. In addition, the dewetting properties of LB monolayers can be used to further achieve patterning within the range of micrometers to tens of nanometers without a predefined template. The LB method should allow for easy integration of nanomaterials into current manufacturing schemes, in addition to fast device prototyping and multiplexing capability.     

Carbon nanostructures as nerve scaffolds for repairing large gaps in severed nerves

As the field of nerve tissue engineering advances, new biomaterials and structures are required to improve the regeneration of damaged nerves. Carbon nanostructures have been recognized as potential candidates to develop neural prostheses due to their one-dimensional nanostructures and similar nanoscale dimensions to neuritis as well as their unique electrical and mechanical properties when being used as a scaffold. This review addresses the promising application of carbon nanostructures in the repair of injured nerves. As a new viewpoint, the possibility of utilizing carbon nanostructures to repair a long gap in a severed nerve will be discussed as well.     

Morphology control and optical properties of SiGe nanostructures grown on glass substrate

With the rapid progress of nanotechnology, nanostructures with different morphologies have been realized, which may be very promising to enhance the performance of semiconductor devices. In this study, SiGe nanostructures with several kinds of configurations have been synthesized through a chemical vapor deposition process. By controlling growth conditions, different SiGe nanostructures can be easily tuned. Structures and compositions of the nanostructures were determined by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The optical properties of various SiGe nanostructures revealed some dependence with their morphologies, which may be suitable for solar cell applications. The control of the SiGe morphology on nanoscale provides a convenient route to produce diverse SiGe nanostructures and creates new opportunities to realize the integration of future devices.     

A general lithography-free method of microscale/nanoscale fabrication and patterning on Si and Ge surfaces

Here, we introduce and give an overview of a general lithography-free method to fabricate silicide and germanide micro-/nanostructures on Si and Ge surfaces through metal-vapor-initiated endoepitaxial growth. Excellent controls on shape and orientation are achieved by adjusting the substrate orientation and growth parameters. Furthermore, micro-/nanoscale pits with controlled morphologies can also be successfully fabricated on Si and Ge surfaces by taking advantage of the sublimation of silicides/germanides. The aim of this brief report is to illustrate the concept of lithography-free synthesis and patterning on surfaces of elemental semiconductors, and the differences and the challenges associated with the Si and the Ge surfaces will be discussed. Our results suggest that this low-cost bottom-up approach is promising for applications in functional nanodevices.     

In situ–Directed Growth of Organic Nanofibers and Nanoflakes: Electrical and Morphological Properties

Organic nanostructures made from organic molecules such as para-hexaphenylene (p-6P) could form nanoscale components in future electronic and optoelectronic devices. However, the integration of such fragile nanostructures with the necessary interface circuitry such as metal electrodes for electrical connection continues to be a significant hindrance toward their large-scale implementation. Here, we demonstrate in situ–directed growth of such organic nanostructures between pre-fabricated contacts, which are source–drain gold electrodes on a transistor platform (bottom-gate) on silicon dioxide patterned by a combination of optical lithography and electron beam lithography. The dimensions of the gold electrodes strongly influence the morphology of the resulting structures leading to notably different electrical properties. The ability to control such nanofiber or nanoflake growth opens the possibility for large-scale optoelectronic device fabrication.     

A direct-write,resistless hard mask for rapid nanoscale patterning of diamond

We introduce a simple, resist-free dry etch mask for producing patterns in diamond, both bulk and thin deposited films. Direct gallium ion beam exposure of the native diamond surface to doses as low as 10¹⁶ cm^?2 forms a top surface hard mask resistant to both oxygen plasma chemical dry etching and, unexpectedly, argon plasma physical dry etching. Gallium implant hard masks of nominal 50 nm thickness demonstrate oxygen plasma etch resistance to over 450 nm depth, or 9:1 selectivity. The process offers significant advantages over direct ion milling of diamond including increased throughput due to separation of patterning and material removal steps, allowing both nanoscale patterning resolution as well as rapid masking of areas approaching millimeter scales. Retention of diamond properties in nanostructures formed by the technique is demonstrated by fabrication of specially shaped nanoindenter tips that can perform imprint pattern transfer at over 14 GPa pressure into gold and silicon surfaces. This resistless technique can be applied to curved and non-planar surfaces for a variety of potential applications requiring high resolution structuring of diamond coatings.     

溶液自组装法制备卟啉纳米材料研究进展

在溶液中,利用自组装方法制备以卟啉化合物为基础的纳米材料具有优良的光物理和光化学性质,在分子器件和人工模拟光合作用等方面具有巨大的应用前景,是目前的研究热点。本文详细介绍了单卟啉组装方法和多卟啉共组装方法,单卟啉组装包括双溶剂法和表面活性剂辅助法两类方法。简要介绍了卟啉自组装纳米材料在集光天线和光催化方面的应用。目前,自组装方法制备的卟啉化合物纳米材料已经出现了丰富的形态,但仍存在不足,即自组装作用机理有待深入研究,且如何将卟啉纳米材料的制备工艺放大并应用于实际,还有待进一步发展。     

From active plasmonic devices to plasmonic molecular electronics

This work is mainly focused on studies combining plasmonic nanostructures and π‐conjugated systems. It describes active molecular plasmonic devices in which π‐conjugated molecules and polymers, grafted on gold nanoparticles, are used to tune the plasmonic properties of metal nanostructures. It also explores two emerging research fields, i.e. plasmonic electrochemistry and plasmonic molecular electronics. In the former, electrochemical reactions are controlled and triggered by plasmons which yield various light‐induced electrochemical reactions at the nanoscale. In the latter, one combines molecular plasmonics and molecular electronics in plasmonic molecular devices. © 2018 Society of Chemical Industry     

Research progress on electronic phase separation in low-dimensional perovskite manganite nanostructures

Perovskite oxide manganites with a general formula of R_1-x AxMnO₃ (where R is a trivalent rare-earth element such as La, Pr, Sm, and A is a divalent alkaline-earth element such as Ca, Sr, and Ba) have received much attention due to their unusual electron-transport and magnetic properties, which are indispensable for applications in microelectronic, magnetic, and spintronic devices. Recent advances in the science and technology have resulted in the feature sizes of microelectronic devices based on perovskite manganite oxides down-scaling into nanoscale dimensions. At the nanoscale, low-dimensional perovskite manganite oxide nanostructures display novel physical properties that are different from their bulk and film counterparts. Recently, there is strong experimental evidence to indicate that the low-dimensional perovskite manganite oxide nanostructures are electronically inhomogeneous, consisting of different spatial regions with different electronic orders, a phenomenon that is named as electronic phase separation (EPS). As the geometry sizes of the low-dimensional manganite nanostructures are reduced to the characteristic EPS length scale (typically several tens of nanometers in manganites), the EPS is expected to be strongly modulated, leading to quite dramatic changes in functionality and more emergent phenomena. Therefore, reduced dimensionality opens a door to the new functionalities in perovskite manganite oxides and offers a way to gain new insight into the nature of EPS. During the past few years, much progress has been made in understanding the physical nature of the EPS in low-dimensional perovskite manganite nanostructures both from experimentalists and theorists, which have a profound impact on the oxide nanoelectronics. This nanoreview covers the research progresses of the EPS in low-dimensional perovskite manganite nanostructures such as nanoparticles, nanowires/nanotubes, and nanostructured films and/or patterns. The possible physical origins of the EPS are also discussed from the signatures of electronic inhomogeneities as well as some theoretical scenarios, to shed light on understanding this phenomenon. Finally, the perspectives to the future researches in this area are also outlined.     

Controllable synthesis of ZnO nanostructures on the Si substrate by a hydrothermal route

In this paper, controllable synthesis of various ZnO nanostructures was achieved via a simple and cost-effective hydrothermal process on the Si substrate. The morphology evolution of the ZnO nanostructures was well monitored by tuning hydrothermal growth parameters, such as the seed layer, solution concentration, reaction temperature, and surfactant. X-ray diffraction and photoluminescence measurements reveal that crystal quality and optical properties crucially depend on the morphology of the ZnO nanostructures. The ease of synthesis and convenience to tune morphology and optical properties bring this approach great potential for nanoscale applications.     

Fabrication of high aspect ratio nanostructures using capillary force lithography

A new ultraviolet (UV) curable mold consisting of functionalized polyurethane with acrylate group (MINS101m, Minuta Tech.) has recently been introduced as an alternative to replace polydimethylsiloxane (PDMS) mold for sub-100-nm lithography. Here, we demonstrate that this mold allows for fabrication of various high aspect ratio nanostructures with an aspect ratio as high as 4.4 for 80 nm nanopillars. For the patterning method, we used capillary force lithography (CFL) involving direct placement of a polyurethane acrylate mold onto a spin-coated polymer film followed by raising the temperature above the glass transition temperature of the polymer (T_g). For the patterning materials, thermoplastic resins such as polystyrene (PS) and poly(methyl methacrylate) (PMMA) and a zinc oxide (ZnO) precursor were used. For the polymer, micro/nanoscale hierarchical structures were fabricated by using sequential application of the same method, which is potentially useful for mimicking functional surfaces such as lotus leaf.     

Doping dependent crystal structures and optoelectronic properties of n-type CdSe:Ga nanowries

Although CdSe nanostructures possess excellent electrical and optical properties, efforts to make nano-optoelectronic devices from CdSe nanostructures have been hampered by the lack of efficient methods to rationally control their structural and electrical characteristics. Here, we report CdSe nanowires (NWs) with doping dependent crystal structures and optoelectronic properties by using gallium (Ga) as the efficient n-type dopant via a simple thermal co-evaporation method. The phase change of CdSe NWs from wurtzite to zinc blende with increased doping level is observed. Systematical measurements on the transport properties of the CdSe:Ga NWs reveal that the NW conductivity could be tuned in a wide range of near nine orders of magnitude by adjusting the Ga doping level and a high electron concentration up to 4.5 × 10(19) cm(-3) is obtained. Moreover, high-performance top-gate field-effect transistors are constructed based on the individual CdSe:Ga NWs by using high-κ HfO(2) as the gate dielectric. The great potential of the CdSe:Ga NWs as high-sensitive photodetectors and nanoscale light emitters is also exploited, revealing the promising applications of the CdSe:Ga NWs in new-generation nano-optoelectronics.     

Symmetry of Bioinspired Short Peptide Nanostructures and Their Basic Physical Properties

Supramolecular bioinspired peptide nanostructures are considered as a new frontier in materials science and engineering. The nano-crystalline packing of various peptide nanostructures, and especially those lacking a center of symmetry at the nanoscale, give rise to exceptional physical properties. Specifically, native aromatic diphenylalanine (FF) and aliphatic dileucine (LL) based nanotubes, which are related to hexagonal and orthorhombic non-centrosymmetric crystalline groups respectively, exhibit fundamental physical phenomena, such as piezoelectricity and second harmonic generation (SHG). This review covers our latest findings on the physical properties of FF and LL nanostructures. We show that heat treatment at the temperature range of 140–180 °C induces irreversible phase transition in FF and LL nanotubes, wherein all their physical properties and structure at all levels (molecular, electronic, optical, space symmetry, morphology, wettability) change. Using high resolution microscopy tools, based on Kelvin probe force microscopy (KPFM), piezoresponse force microscopy (PFM), and SHG, as well as Raman spectroscopy, we demonstrate that the phase-transition phenomena in FF and LL nanotubes leads to full reconstruction and reassembling of native open-end nanotubes into new fiber-like structures, followed by deep variation of non-centrosymmetric to centrosymmetric space symmetry. As a result, the newly generated centrosymmetric phase in FF and LL nanostructures demonstrates neither piezoelectric effect nor nonlinear optical activity.     

Solution-phase synthesis of metal and/or semiconductor homojunction/heterojunction nanomaterials

The design and architecture of programmable metal-semiconductor nanostructures with excellent optoelectronic properties from metal and semiconductor building blocks with nanoscale dimensions have been a key aim of material scientists due to their central roles in the fabrication of electronic, optical, and optoelectronic nanodevices. This review focuses on the latest advances in the solution-phase synthesis of metal and/or semiconductor homojunction/heterojunction nanomaterials. It begins with the simplest construction of metal/metal and semiconductor/semiconductor homojunctions, and then highlights the synthetic design of metal/metal and semiconductor/semiconductor heterojunction nanostructures with different building blocks. Special emphasis is placed on metal/semiconductor heterojunction nanomaterials, which are the most challenging and promising nanomaterials for future applications in optoelectronic nanodevices. Finally, this review concludes with personal perspectives on the directions for future research in this field.     

Monodispersed and size-controlled multibranched gold nanoparticles with nanoscale tuning of surface morphology

A novel seed-mediated synthetic route to produce multibranched gold nanoparticles is reported, in which it is possible to precisely tune both their size and nanostructuration, while maintaining an accurate level of monodispersion. The nanoscale control of surface nanoroughness/branching, ranging from small bud-like features to elongated spikes, allows to obtain fine tuning of the nanoparticle optical properties, up to the red and near-IR region of the spectrum. Such anisotropic nanostructures were demonstrated to be excellent candidates for SERS applications, showing significantly higher signals with respect to the standard spherical nanoparticles.     

Scanning tunneling microscopy and spectroscopy of supported nanostructures

Recent advances in low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) have provided new opportunities for the investigation of the local geometric, electronic, magnetic, and optical properties of nanostructures. This review focuses on the presentation and discussion of single molecules, supramolecular assemblies, and other nanostructures; all research results obtained in our laboratory. The emphasis is directed to the observation of new effects, where the properties of matter at the nanoscale differ from those at the mesoscopic or macroscopic scale: small is different. This fact is illustrated for the conservation of chirality in a hierarchical supramolecular assembly of organic molecules and for local light emission from supported molecules. The latter indicates a possible route towards an optical spectroscopic analysis on the scale of single molecules.     

Patterning High Explosives at the Nanoscale

For the first time, we have shown that spin coating and Dip pen nanolithography (DPN^TM) are simple methods of preparing energetic materials such as PETN and HMX on the nanoscale, requiring no heating of the energetic material. Nanoscale patterning has been demonstrated by the DPN method while continuous thin films were produced using the spin coating method. Results are presented for preparing continuous PETN thin films of nanometer thickness by the spin coating method and for controlling the architecture of arbitrary nanoscale patterns of PETN and HMX by the DPN method. These methods are simple for patterning energetic materials and can be extended beyond PETN and HMX, opening the door for fundamental studies at the nanoscale.