Exploiting nanostructure-thin film interfaces in advanced sensor device configurations

In this report, we present a study on the exploitation of nanostructure-thin film interfaces. Here, the objective is to utilize such interfaces for developing nanostructures for advanced sensing devices, while using state-of-the-art microelectronic technology that enables batch production. In this context, growth of ZnO nanostructures on the GaN/AlGaN heterostructure layers was studied. A fabrication process, based on a hydrothermal growth method, was used for preparing the interfaces of nanostructured thin film. Samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) and obtained results suggested near epitaxial quality of the hetero-interface. Field-effect transistors (FETs) based on ZnO nanorods/GaN heterostructures were fabricated and tested in a controlled gas environment. Thus, it was demonstrated that nanostructures could be exploited in unconventional ways by employing them in scalable and batch-producible conventional semiconductor devices.     

Graphene on cubic-SiC

The outstanding properties of graphene make it a top candidate for replacing silicon in future electronic devices. However, for technological applications, graphene must be synthesized on the surface of wide-gap semiconductors. In this review, we focus on graphene synthesized on single-crystalline cubic-SiC thin films epitaxially grown on standard silicon wafers. These low-cost substrates are commercially available and fully compatible with existing silicon technologies. The results obtained in recent years demonstrate that few-layer graphene synthesized on cubic-SiC substrates possesses the atomic structure and electronic properties of quasi-free-standing graphene. However, according to data obtained by various techniques, few-layer graphene on cubic-SiC consists of nanodomains connected to one another through nanodomain boundaries. After optimization of the preparation procedures, such a nanostructured graphene overlayer can represent a very promising system for the development of new graphene-based electronic devices. In particular, recent works demonstrate that continuous few-layer graphene with self-aligned nanodomain boundaries can be synthesized on vicinal SiC(0 0 1) substrates. Electrical measurements show the opening of a transport gap in nanostructured trilayer graphene synthesized on SiC/2°-off Si(0 0 1) wafers. This development may lead to new tunable electronic nanostructures made from graphene on cubic-SiC, opening up opportunities for a wide range of applications.     

Graphene edge lithography

Fabrication of graphene nanostructures is of importance for both investigating their intrinsic physical properties and applying them into various functional devices. In this paper, we report a scalable fabrication approach for graphene nanostructures. Compared with conventional lithographic fabrication techniques, this new approach uses graphene edges as the templates or masks and offers advantage in technological simplicity and capability of creating small features below 10 nm scale. Moreover, mask layers used in the fabrication process could be simultaneously used as the dielectric layers for top-gated devices. The as-fabricated graphene nanoribbons (GNRs) are of high quality with the carrier mobility ～400 cm(2)/(V s) for typical 15 nm wide ribbons. Our technique allows easy and reproducible fabrication of various graphene nanostructures, such as ribbons and rings, and can be potentially extended to other materials and systems by use of their edges or facets as templates.     

Large area tunable arrays of graphene nanodots fabricated using diblock copolymer micelles

Nanostructured graphenes such as nanoribbons, nanomeshes, and nanodots have attracted a great deal of attention in relation to graphene-based semiconductor devices. The block copolymer micellar approach is a promising bottom-up technique for generating large area nanostructures of various materials without using sophisticated electron-beam lithography. Here we demonstrate the fabrication of an array of graphene nanodots with tunable size and inter-distance with the utilization of a monolayer of diblock copolymer micelles. Au nanoparticles were synthesized in the micellar cores and effectively worked as shielding nanostructures in generating graphene nanodots by oxygen plasma etching. We also controlled the radius and inter-distance of graphene nanodots simply through the molecular weight of the copolymers.     

Quasiparticle band gap engineering of graphene and graphone on hexagonal boron nitride substrate

Graphene holds great promise for post-silicon electronics; however, it faces two main challenges: opening up a band gap and finding a suitable substrate material. In principle, graphene on hexagonal boron nitride (hBN) substrate provides a potential system to overcome these challenges. Recent theoretical and experimental studies have provided conflicting results: while theoretical studies suggested a possibility of a finite band gap of graphene on hBN, recent experimental studies find no band gap. Using the first-principles density functional method and the many-body perturbation theory, we have studied graphene on hBN substrate. A Bernal stacked graphene on hBN has a band gap on the order of 0.1 eV, which disappears when graphene is misaligned with respect to hBN. The latter is the likely scenario in realistic devices. In contrast, if graphene supported on hBN is hydrogenated, the resulting system (graphone) exhibits band gaps larger than 2.5 eV. While the band gap opening in graphene/hBN is due to symmetry breaking and is vulnerable to slight perturbation such as misalignment, the graphone band gap is due to chemical functionalization and is robust in the presence of misalignment. The band gap of graphone reduces by about 1 eV when it is supported on hBN due to the polarization effects at the graphone/hBN interface. The band offsets at graphone/hBN interface indicate that hBN can be used not only as a substrate but also as a dielectric in the field effect devices employing graphone as a channel material. Our study could open up new way of band gap engineering in graphene based nanostructures.     

Progress and Design Concerns of Nanostructured Solar Energy Harvesting Devices

Integrating devices with nanostructures is considered a promising strategy to improve the performance of solar energy harvesting devices such as photovoltaic (PV) devices and photo‐electrochemical (PEC) solar water splitting devices. Extensive efforts have been exerted to improve the power conversion efficiencies (PCE) of such devices by utilizing novel nanostructures to revolutionize device structural designs. The thicknesses of light absorber and material consumption can be substantially reduced because of light trapping with nanostructures. Meanwhile, the utilization of nanostructures can also result in more effective carrier collection by shortening the photogenerated carrier collection path length. Nevertheless, performance optimization of nanostructured solar energy harvesting devices requires a rational design of various aspects of the nanostructures, such as their shape, aspect ratio, periodicity, etc. Without this, the utilization of nanostructures can lead to compromised device performance as the incorporation of these structures can result in defects and additional carrier recombination. The design guidelines of solar energy harvesting devices are summarized, including thin film non‐uniformity on nanostructures, surface recombination, parasitic absorption, and the importance of uniform distribution of photo‐generated carriers. A systematic view of the design concerns will assist better understanding of device physics and benefit the fabrication of high performance devices in the future.     

Strain-engineering of band gaps in piezoelectric boron nitride nanoribbons

Two-dimensional atomic sheets such as graphene and boron nitride monolayers represent a new class of nanostructured materials for a variety of applications. However, the intrinsic electronic structure of graphene and h-BN atomic sheets limits their direct application in electronic devices. By first-principles density functional theory calculations we demonstrate that band gap of zigzag BN nanoribbons can be significantly tuned under uniaxial tensile strain. The unexpected sensitivity of band gap results from reduced orbital hybridization upon elastic strain. Furthermore, sizable dipole moment and piezoelectric effect are found in these ribbons owing to structural asymmetry and hydrogen passivation. This will offer new opportunities to optimize two-dimensional nanoribbons for applications such as electronic, piezoelectric, photovoltaic, and opto-electronic devices.     

Large Photothermal Effect in Sub‐40 nm h‐BN Nanostructures Patterned Via High‐Resolution Ion Beam

The controlled nanoscale patterning of 2D materials is a promising approach for engineering the optoelectronic, thermal, and mechanical properties of these materials to achieve novel functionalities and devices. Herein, high‐resolution patterning of hexagonal boron nitride (h‐BN) is demonstrated via both helium and neon ion beams and an optimal dosage range for both ions that serve as a baseline for insulating 2D materials is identified. Through this nanofabrication approach, a grating with a 35 nm pitch, individual structure sizes down to 20 nm, and additional nanostructures created by patterning crystal step edges are demonstrated. Raman spectroscopy is used to study the defects induced by the ion beam patterning and is correlated to scanning probe microscopy. Photothermal and scanning near‐field optical microscopy measure the resulting near‐field absorption and scattering of the nanostructures. These measurements reveal a large photothermal expansion of nanostructured h‐BN that is dependent on the height to width aspect ratio of the nanostructures. This effect is attributed to the large anisotropy of the thermal expansion coefficients of h‐BN and the nanostructuring implemented. The photothermal expansion should be present in other van der Waals materials with large anisotropy and can lead to applications such as nanomechanical switches driven by light.     

Graphene-enabled silver nanoantenna sensors

Silver is the ideal material for plasmonics because of its low loss at optical frequencies but is often replaced by a more lossy metal, gold. This is because of silver's tendency to tarnish and roughen, forming Ag(2)S on its surface, dramatically diminishing optical properties and rendering it unreliable for applications. By passivating the surface of silver nanostructures with monolayer graphene, atmospheric sulfur containing compounds are unable to penetrate the graphene to degrade the surface of the silver. Preventing this sulfidation eliminates the increased material damping and scattering losses originating from the unintentional Ag(2)S layer. Because it is atomically thin, graphene does not interfere with the ability of localized surface plasmons to interact with the environment in sensing applications. Furthermore, after 30 days graphene-passivated silver (Ag-Gr) nanoantennas exhibit a 2600% higher sensitivity over that of bare Ag nanoantennas and 2 orders of magnitude improvement in peak width endurance. By employing graphene in this manner, the excellent optical properties and large spectral range of silver can be functionally utilized in a variety of nanoscale plasmonic devices and applications.     

Effects of nanostructured back reflectors on the external quantum efficiency in thin film solar cells

Hydrogenated amorphous Si ( α-Si:H) is a promising material for photovoltaic applications due to its low cost, high abundance, long lifetime, and non-toxicity. We demonstrate a device designed to investigate the effect of nanostructured back reflectors on quantum efficiency in photovoltaic devices. We adopt a superstrate configuration so that we may use conventional industrial light trapping strategies for thin film solar cells as a reference for comparison. We controlled the nanostructure parameters via a wafer-scale self-assembly technique and systematically studied the relation between nanostructure size and photocurrent generation. The gain/loss transition at short wavelengths showed red-shifts with decreasing nanostructure scale. In the infrared region the nanostructured back reflector shows large photocurrent enhancement with a modified feature scale. This device geometry is a useful archetype for investigating absorption enhancement by nanostructures.     

Chemically Integrated Inorganic‐Graphene Two‐Dimensional Hybrid Materials for Flexible Energy Storage Devices

State‐of‐the‐art energy storage devices are capable of delivering reasonably high energy density (lithium ion batteries) or high power density (supercapacitors). There is an increasing need for these power sources with not only superior electrochemical performance, but also exceptional flexibility. Graphene has come on to the scene and advancements are being made in integration of various electrochemically active compounds onto graphene or its derivatives so as to utilize their flexibility. Many innovative synthesis techniques have led to novel graphene‐based hybrid two‐dimensional nanostructures. Here, the chemically integrated inorganic‐graphene hybrid two‐dimensional materials and their applications for energy storage devices are examined. First, the synthesis and characterization of different kinds of inorganic‐graphene hybrid nanostructures are summarized, and then the most relevant applications of inorganic‐graphene hybrid materials in flexible energy storage devices are reviewed. The general design rules of using graphene‐based hybrid 2D materials for energy storage devices and their current limitations and future potential to advance energy storage technologies are also discussed.     

Metallic nanowire-graphene hybrid nanostructures for highly flexible field emission devices

We report a simple but efficient method to prepare metallic nanowire-graphene (MN-G) hybrid nanostructures at a low temperature and show its application to the fabrication of flexible field emission devices. In this method, a graphene layer was transferred onto an anodic alumina oxide template, and vertically aligned Au nanowires were grown on the graphene surface via electrodeposition method. As a proof of concept, we demonstrated the fabrication of flexible field emission devices, where the MN-G hybrid nanostructures and another graphene layer on PDMS substrates were utilized as a cathode and an anode for highly flexible devices, respectively. Our field emission device exhibited stable and high field emission currents even when bent down to the radius of curvature of 25 mm. This MN-G hybrid nanostructure should prove tremendous flexibility for various applications such as bio-chemical sensors, field emission devices, pressure sensors and battery electrodes.     

Droplet Transport on a Nano‐ and Microstructured Surface with a Wettability Gradient in Low‐Temperature or High‐Humidity Environments

Directional driving of a droplet can be achieved on a gradient‐exhibiting, nanostructured microhump (GNMH) surface at low temperature and high humidity. The GNMH surface is fabricated using a commercial carbon fiber plate with an array of microscale hump structures; nanotechniques are used to form varying nanostructures on the microhump array, producing the micro‐ and nanostructured surface. The different nanostructures result in a wettability gradient along the surface, enabling droplet transport with the help of vibration—even at low temperature or high humidity. In contrast, simply nanostructured surfaces or microstructured surfaces that also have a wettable gradient do not enable droplet transport at low temperature or high humidty. In a range of subzero temperatures or in a range of high‐humidity conditions, the GNMH surface retains its superhydrophobicity and ability for directional droplet transport along its wettability gradient. These results may assist in the design of surfaces required for cold environments, such as microreactors, chemical analytic devices, and sensors.     

Enhancing the supercapacitor performance of graphene/MnO2 nanostructured electrodes by conductive wrapping

MnO2 is considered one of the most promising pseudocapactive materials for high-performance supercapacitors given its high theoretical specific capacitance, low-cost, environmental benignity, and natural abundance. However, MnO2 electrodes often suffer from poor electronic and ionic conductivities, resulting in their limited performance in power density and cycling. Here we developed a "conductive wrapping" method to greatly improve the supercapacitor performance of graphene/MnO2-based nanostructured electrodes. By three-dimensional (3D) conductive wrapping of graphene/MnO2 nanostructures with carbon nanotubes or conducting polymer, specific capacitance of the electrodes (considering total mass of active materials) has substantially increased by ～20% and ～45%, respectively, with values as high as ～380 F/g achieved. Moreover, these ternary composite electrodes have also exhibited excellent cycling performance with >95% capacitance retention over 3000 cycles. This 3D conductive wrapping approach represents an exciting direction for enhancing the device performance of metal oxide-based electrochemical supercapacitors and can be generalized for designing next-generation high-performance energy storage devices.     

Nanoenvelopes: Wrapping a Single‐Walled Carbon Nanotube with Graphene using an Atomic Force Microscope

Engineering the morphology and structure of low‐dimensional carbon nanomaterials is important to study their mechanical and electrical properties and even superconductivity. Herein, first the techniques that are used to engineer carbon nanotubes, including manipulation, morphology modification, and fabrication of complex nanostructures, are reviewed. This is followed by a summary of the methods applied to fabricate graphene nanostructures, such as heterostructures and nanoenvelopes of graphene. Lastly, an insight into the applications of low‐dimensional‐carbon‐based electronics is given, such as carbon nanotube (CNT) transistors, graphene‐based nanoenvelopes, and graphene‐contacted CNT field‐effect transistors (FETs), which are promising components in future electronics.     

Capacitive gas and vapor sensors using nanomaterials

An immense number of sensors has been reported in the literature employing various methods for the detection of different gases and vapors. This article summarizes those sensors whose sensing layer is made up of nanostructured materials and a change in capacitance value of device is the key parameter for detecting a gas or vapor. Now-a-days, capacitive sensors are emerging as they consume less power, operate well at room temperature and show decent response and recovery time. The sensing principles, configurations, mechanisms and performances of capacitive sensors based on different nanostructures are summarized and discussed in the current article. Emerging carbon based nanomaterials like carbon nanotube and graphene are also highlighted for capacitive mode detection of gases and vapors. Finally, an outlook of primary challenges in this field are identified and discussed at the end of the review.     

25th Anniversary Article: Hybrid Nanostructures Based on Two‐Dimensional Nanomaterials

Two‐dimensional (2D) nanomaterials, such as graphene and transition metal dichalcogenides (TMDs), receive a lot of attention, because of their intriguing properties and wide applications in catalysis, energy‐storage devices, electronics, optoelectronics, and so on. To further enhance the performance of their application, these 2D nanomaterials are hybridized with other functional nanostructures. In this review, the latest studies of 2D nanomaterial‐based hybrid nanostructures are discussed, focusing on their preparation methods, properties, and applications.     

Heterogeneous graphene nanostructures: ZnO nanostructures grown on large-area graphene layers

In this work, the synthesis and characterization of three-dimensional hetergeneous graphene nanostructures (HGN) comprising continuous large-area graphene layers and ZnO nanostructures, fabricated via chemical vapor deposition, are reported. Characterization of large-area HGN demonstrates that it consists of 1-5 layers of graphene, and exhibits high optical transmittance and enhanced electrical conductivity. Electron microscopy investigation of the three-dimensional heterostructures shows that the morphology of ZnO nanostructures is highly dependent on the growth temperature. It is observed that ordered crystalline ZnO nanostructures are preferably grown along the <0001> direction. Ultraviolet spectroscopy and photoluminescence spectroscopy indicates that the CVD-grown HGN layers has excellent optical properties. A combination of electrical and optical properties of graphene and ZnO building blocks in ZnO-based HGN provides unique characteristics for opportunities in future optoelectronic devices.     

Monolayer Graphene Coupled to a Flexible Plasmonic Nanograting for Ultrasensitive Strain Monitoring

Plasmonically coupled graphene structures have shown great promise for sensing applications. Their complex and cumbersome fabrication, however, has prohibited their widespread application and limited their use to rigid, planar surfaces. Here, a plasmonic sensor based on gold nanowire arrays on an elastomer with an added graphene monolayer is introduced. The stretchable plasmonic nanostructures not only significantly enhance the Raman signal from graphene, but can also be used by themselves as a sensor platform for 2D strain sensing. These nanowire arrays on an elastomer are fabricated by template‐stripping based nanotransfer printing, which enables a simple and fast production of stable nanogratings. The ultrasmooth surfaces of such transferred structures facilitate reliable large‐area transfers of graphene monolayers. The resulting coupled graphene‐nanograting construct exhibits ultrahigh sensitivity to applied strain, which can be detected by shifts in the plasmonic‐enhanced Raman spectrum. Furthermore, this sensor enables the detection of adsorbed molecules on nonplanar surfaces through graphene‐assisted surface enhanced Raman spectroscopy (SERS). The simple fabrication of the plasmonic nanowire array platform and the graphene‐coupled devices have the potential to trigger widespread SERS applications and open up new opportunities for high‐sensitivity strain sensing applications.