High quality epitaxial graphene on 4H-SiC by face-to-face growth in ultra-high vacuum.

Epitaxial graphene on SiC is the most promising substrate for the next generation 2D electronics, due to the possibility to fabricate 2D heterostructures directly on it, opening the door to the use of all technological processes developed for silicon electronics. To obtain a suitable material for large scale applications, it is essential to achieve perfect control of size, quality, growth rate and thickness. Here we show that this control on epitaxial graphene can be achieved by exploiting the face-to-face annealing of SiC in ultra-high vacuum. With this method, Si atoms trapped in the narrow space between two SiC wafers at high temperatures contribute to the reduction of the Si sublimation rate, allowing to achieve smooth and virtually defect free single graphene layers. We analyse the products obtained on both on-axis and off-axis 4H-SiC substrates in a wide range of temperatures (1300 °C-1500 °C), determining the growth law with the help of x-ray photoelectron spectroscopy (XPS). Our epitaxial graphene on SiC has terrace widths up to 10µm (on-axis) and 500 nm (off-axis) as demonstrated by atomic force microscopy and scanning tunnelling microscopy, while XPS and Raman spectroscopy confirm high purity and crystalline quality.

Highly Sensitive NO2 Gas Sensors Based on MoS2@MoO3 Magnetic Heterostructure.

Recently, two-dimensional (2D) materials and their heterostructures have attracted considerable attention in gas sensing applications. In this work, we synthesized 2D MoS2@MoO3 heterostructures through post-sulfurization of α-MoO3 nanoribbons grown via vapor phase transport (VPT) and demonstrated highly sensitive NO2 gas sensors based on the hybrid heterostructures. The morphological, structural, and compositional properties of the MoS2@MoO3 hybrids were studied by a combination of advanced characterization techniques revealing a core-shell structure with the coexistence of 2H-MoS2 multilayers and intermediate molybdenum oxysulfides on the surface of α-MoO3. The MoS2@MoO3 hybrids also exhibit room-temperature ferromagnetism, revealed by vibrating sample magnetometry (VSM), as a result of the sulfurization process. The MoS2@MoO3 gas sensors display a p-type-like response towards NO2 with a detection limit of 0.15 ppm at a working temperature of 125 °C, as well as superb selectivity and reversibility. This p-type-like sensing behavior is attributed to the heterointerface of MoS2-MoO3 where interfacial charge transfer leads to a p-type inversion layer in MoS2, and is enhanced by magnetic dipole interactions between the paramagnetic NO2 and the ferromagnetic sensing layer. Our study demonstrates the promising application of 2D molybdenum hybrid compounds in gas sensing applications with a unique combination of electronic and magnetic properties.

Plasma-Induced Nanocrystalline Domain Engineering and Surface Passivation in Mesoporous Chalcogenide Semiconductor Thin Films.

The synthesis of highly crystalline mesoporous materials is key to realizing high-performance chemical and biological sensors and optoelectronics. However, minimizing surface oxidation and enhancing the domain size without affecting the porous nanoarchitecture are daunting challenges. Herein, we report a hybrid technique that combines bottom-up electrochemical growth with top-down plasma treatment to produce mesoporous semiconductors with large crystalline domain sizes and excellent surface passivation. By passivating unsaturated bonds without incorporating any chemical or physical layers, these films show better stability and enhancement in the optoelectronic properties of mesoporous copper telluride (CuTe) with different pore diameters. These results provide exciting opportunities for the development of long-term, stable, and high-performance mesoporous semiconductor materials for future technologies.

MoS2/Epitaxial graphene layered electrodes for solid-state supercapacitors.

The potential of transition metal dichalcogenides such as MoS2 for energy storage has been significantly limited so far by the lack of conductivity and structural stability. Employing highly conductive, graphitic materials in combination with transition metal dichalcogenides can address this gap. Here, we explore the use of a layered electrode structure for solid-state supercapacitors, made of MoS2 and epitaxial graphene (EG) on cubic silicon carbide for on-silicon energy storage. We show that the energy storage of the solid-state supercapacitors can be significantly increased by creating layered MoS2/graphene electrodes, yielding a substantial improvement as compared to electrodes using either EG or MoS2 alone. We conclude that the conductivity of EG and the growth morphology of MoS2 on graphene play an enabling role in the successful use of transition metal dichalcogenides for on-chip energy storage.

Covalent Graphene-MOF Hybrids for High-Performance Asymmetric Supercapacitors.

In this work, the covalent attachment of an amine functionalized metal-organic framework (UiO-66-NH2  = Zr6 O4 (OH)4 (bdc-NH2 )6 ; bdc-NH2  = 2-amino-1,4-benzenedicarboxylate) (UiO-Universitetet i Oslo) to the basal-plane of carboxylate functionalized graphene (graphene acid = GA) via amide bonds is reported. The resultant GA@UiO-66-NH2 hybrid displayed a large specific surface area, hierarchical pores and an interconnected conductive network. The electrochemical characterizations demonstrated that the hybrid GA@UiO-66-NH2 acts as an effective charge storing material with a capacitance of up to 651 F g-1 , significantly higher than traditional graphene-based materials. The results suggest that the amide linkage plays a key role in the formation of a π-conjugated structure, which facilitates charge transfer and consequently offers good capacitance and cycling stability. Furthermore, to realize the practical feasibility, an asymmetric supercapacitor using a GA@UiO-66-NH2 positive electrode with Ti3 C2 TX MXene as the opposing electrode has been constructed. The cell is able to deliver a power density of up to 16 kW kg-1 and an energy density of up to 73 Wh kg-1 , which are comparable to several commercial devices such as Pb-acid and Ni/MH batteries. Under an intermediate level of loading, the device retained 88% of its initial capacitance after 10 000 cycles.

Synthesis and characterization of WS2/graphene/SiC van der Waals heterostructures via WO3-x thin film sulfurization.

Van der Waals heterostructures of monolayer transition metal dichalcogenides (TMDs) and graphene have attracted keen scientific interest due to the complementary properties of the materials, which have wide reaching technological applications. Direct growth of uniform, large area TMDs on graphene substrates by chemical vapor deposition (CVD) is limited by slow lateral growth rates, which result in a tendency for non-uniform multilayer growth. In this work, monolayer and few-layer WS2 was grown on epitaxial graphene on SiC by sulfurization of WO3-x thin films deposited directly onto the substrate. Using this method, WS2 growth was achieved at temperatures as low as 700 °C - significantly less than the temperature required for conventional CVD. Achieving long-range uniformity remains a challenge, but this process could provide a route to synthesize a broad range of TMD/graphene van der Waals heterostructures with novel properties and functionality not accessible by conventional CVD growth.

Photonic Fractal Metamaterials: A Metal-Semiconductor Platform with Enhanced Volatile-Compound Sensing Performance.

Advance of photonics media is restrained by the lack of structuring techniques for the 3D fabrication of active materials with long-range periodicity. A methodology is reported for the engineering of tunable resonant photonic media with thickness exceeding the plasmonic near-field enhancement region by more than two orders of magnitude. The media architecture consists of a stochastically ordered distribution of plasmonic nanocrystals in a fractal scaffold of high-index semiconductors. This plasmonic-semiconductor fractal media supports the propagation of surface plasmons with drastically enhanced intensity over multiple length scales, overcoming the 2D limitations of established metasurface technologies. The fractal media are used for the fabrication of plasmonic optical gas sensors, achieving a limit of detection of 0.01 vol% at room temperature and sensitivity up to 1.9 nm vol%-1 , demonstrating almost a fivefold increase with respect to an optimized planar geometry. Beneficially to their implementation, the self-assembly mechanism of this fractal architecture allows fabrication of micrometer-thick media over surfaces of several square centimeters in a few seconds. The designable optical features and intrinsic scalability of these photonic fractal metamaterials provide ample opportunities for applications, bridging across transformation optics, sensing, and light harvesting.

Simple Method for Estimating the Surface Area of Layered Graphene-Based Thin Films.

Thin films, papers, or foils produced from graphene-based materials have been the focus of considerable research interest in recent years. They have a range of applications including energy storage, selective filtration of liquids, and gas storage. For all of these applications, the critical attribute of the films is their pore volume. However, there remains a considerable challenge around characterizing the accessible microscopic surface area of the materials in their intended state of application. In this work, an image-processing-based approach is presented for estimating the lower threshold of specific surface area for graphene-based films that have a typical multilayered structure. Canny edge detection is used together with tortuosity measurements to infer sheet areas from layer edges. The method serves as a simple independent characterization technique. Specific surface area values predicted for a range of similar films vary by less than 4× the reported values, which vary by >1.1×103 in range.

Multiscale Plasma-Catalytic On-Surface Assembly.

Controlled modification of surfaces is one of the key pursuits of the nanoscience and nanotechnology fields, allowing for the fabrication of bespoke materials with targeted functionalities. However, many surface modifications currently require painstakingly precise and/or energy intensive processing to implement, and are thus limited in scope and scale. Here, a concept which can enhance the capacity for control of surfaces is introduced: plasma-assisted nucleation and self-assembly at atomic to nanoscales, scalable at atmospheric pressures.

Metal-Organic Frameworks/Conducting Polymer Hydrogel Integrated Three-Dimensional Free-Standing Monoliths as Ultrahigh Loading Li-S Battery Electrodes.

The lithium-sulfur (Li-S) system is a promising material for the next-generation of high energy density batteries with application extending from electrical vehicles to portable devices and aeronautics. Despite progress, the energy density of current Li-S technologies is still below that of conventional intercalation-type cathode materials due to limited stability and utilization efficiency at high sulfur loading. Here, we present a conducting polymer hydrogel integrated highly performing free-standing three-dimensional (3D) monolithic electrode architecture for Li-S batteries with superior electrochemical stability and energy density. The electrode layout consists of a highly conductive three-dimensional network of N,P codoped carbon with well-dispersed metal-organic framework nanodomains of ZIF-67 and HKUST-1. The hierarchical monolithic 3D carbon networks provide an excellent environment for charge and electrolyte transport as well as mechanical and chemical stability. The electrically integrated MOF nanodomains significantly enhance the sulfur loading and retention capabilities by inhibiting the release of lithium polysulfide specificities as well as improving the charge transfer efficiency at the electrolyte interface. Our optimal 3D carbon-HKUST-1 electrode architecture achieves a very high areal capacity of >16 mAh cm-2 and volumetric capacity (CV) of 1230.8 mAh cm-3 with capacity retention of 82% at 0.2C for over 300 cycles, providing an attractive candidate material for future high-energy density Li-S batteries.

Adsorption, Deprotonation, and Decarboxylation of Isophthalic Acid on Cu(111).

The surface-assisted reaction of rationally designed organic precursors is an emerging approach toward fabricating atomically precise nanostructures. Recently, on-surface decarboxylation has attracted attention due to its volatile by-products, which tend to leave the surface during the reaction means only the desired products are retained on the surface. However, in addition to acting as the reactive site, the carboxylic acid groups play a vital role in the adsorption configuration of small-molecule molecular precursors and therefore in the reaction pathways. Here, scanning tunnelling microscopy (STM), synchrotron radiation photoelectron spectroscopy (SRPES), and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy have been employed to characterize the monodeprotonated, fully deprotonated, and decarboxylated products of isophthalic acid (IPA) on Cu(111). IPA is partially reacted (monodeprotonated) upon adsorption on Cu(111) at room temperature. Angular-dependent X-ray photoelectron spectroscopy reveals that IPA initially anchors to the surface via the carboxylate group. After annealing, the molecule fully deprotonates and reorients so that it anchors to the surface via both carboxylate groups in a bipodal configuration. NEXAFS confirms that the molecule is tilted upon adsorption and after full deprotonation. Following decarboxylation, the flat-lying molecule forms into oligomeric motifs on the surface. This work demonstrates the importance of molecular adsorption geometry for on-surface reactions.

A Review of Supercapacitors Based on Graphene and Redox-Active Organic Materials.

Supercapacitors are a highly promising class of energy storage devices due to their high power density and long life cycle. Conducting polymers (CPs) and organic molecules are potential candidates for improving supercapacitor electrodes due to their low cost, large specific pseudocapacitance and facile synthesis methods. Graphene, with its unique two-dimensional structure, shows high electrical conductivity, large specific surface area and outstanding mechanical properties, which makes it an excellent material for lithium ion batteries, fuel cells and supercapacitors. The combination of CPs and graphene as electrode material is expected to boost the properties of supercapacitors. In this review, we summarize recent reports on three different CP/graphene composites as electrode materials for supercapacitors, discussing synthesis and electrochemical performance. Novel flexible and wearable devices based on CP/graphene composites are introduced and discussed, with an eye to recent developments and challenges for future research directions.

Electron effective attenuation length in epitaxial graphene on SiC.

The inelastic mean free path (IMFP) for carbon-based materials is notoriously challenging to model, and moving from bulk materials to 2D materials may exacerbate this problem, making the accurate measurements of IMFP in 2D carbon materials critical. The overlayer-film method is a common experimental method to estimate IMFP by measuring electron effective attenuation length (EAL). This estimation relies on an assumption that elastic scattering effects are negligible. We report here an experimental measurement of electron EAL in epitaxial graphene on SiC using photoelectron spectroscopy over an electron kinetic energy range of 50-1150 eV. We find a significant effect of the interface between the 2D carbon material and the substrate, indicating that the attenuation length in the so-called 'buffer layer' is smaller than for free-standing graphene. Our results also suggest that the existing models for estimating IMFPs may not adequately capture the physics of electron interactions in 2D materials.

Optimization of Mo/Cr bilayer back contacts for thin-film solar cells.

Molybdenum (Mo) is the most commonly used material as back contact in thin-film solar cells. Adhesion of Mo film to soda-lime glass (SLG) substrate is crucial to the performance of solar cells. In this study, an optimized bilayer structure made of a thin layer of Mo on an ultra-thin chromium (Cr) adhesion layer is used as the back contact for a copper zinc tin sulfide (CZTS) thin-film solar cell on a SLG substrate. DC magnetron sputtering is used for deposition of Mo and Cr films. The conductivity of Mo/Cr bilayer films, their microstructure and surface morphology are studied at different deposition powers and working pressures. Good adhesion to the SLG substrate has been achieved by means of an ultra-thin Cr layer under the Mo layer. By optimizing the deposition conditions we achieved low surface roughness, high optical reflectance and low sheet resistivity while we could decrease the back contact thickness to 600 nm. That is two thirds to half of the thickness that is currently being used for bilayer and single layer back contact for thin-film solar cells. We demonstrate the excellent properties of Mo/Cr bilayer as back contact of a CZTS solar cell.

Electrospun one-dimensional nanostructures: a new horizon for gas sensing materials.

Electrospun one-dimensional (1D) nanostructures are rapidly emerging as key enabling components in gas sensing due to their unique electrical, optical, magnetic, thermal, mechanical and chemical properties. 1D nanostructures have found applications in numerous areas, including healthcare, energy storage, biotechnology, environmental monitoring, and defence/security. Their enhanced specific surface area, superior mechanical properties, nanoporosity and improved surface characteristics (in particular, uniformity and stability) have made them important active materials for gas sensing applications. Such highly sensitive and selective elements can be embedded in sensor nodes for internet-of-things applications or in mobile systems for continuous monitoring of air pollutants and greenhouse gases as well as for monitoring the well-being and health in everyday life. Herein, we review recent developments of gas sensors based on electrospun 1D nanostructures in different sensing platforms, including optical, conductometric and acoustic resonators. After explaining the principle of electrospinning, we classify sensors based on the type of materials used as an active sensing layer, including polymers, metal oxide semiconductors, graphene, and their composites or their functionalized forms. The material properties of these electrospun fibers and their sensing performance toward different analytes are explained in detail and correlated to the benefits and limitations for every approach.

Nanostructured Dielectric Fractals on Resonant Plasmonic Metasurfaces for Selective and Sensitive Optical Sensing of Volatile Compounds.

Advances in the understanding and fabrication of plasmonic nanostructures have led to a plethora of unprecedented optoelectronic and optochemical applications. Plasmon resonance has found widespread use in efficient optical transducers of refractive index changes in liquids. However, it has proven challenging to translate these achievements to the selective detection of gases, which typically adsorb non-specifically and induce refractive index changes below the detection limit. Here, it's shown that integration of tailored fractals of dielectric TiO2 nanoparticles on a plasmonic metasurface strongly enhances the interaction between the plasmonic field and volatile organic molecules and provides a means for their selective detection. Notably, this superior optical response is due to the enhancement of the interaction between the dielectric fractals and the plasmonic metasurface for thickness of up to 1.8 µm, much higher than the evanescent plasmonic near-field (≈30 nm) . Optimal dielectric-plasmonic structures allow measurements of changes in the refractive index of the gas mixture down to <8 × 10-6 at room temperature and selective identification of three exemplary volatile organic compounds. These findings provide a basis for the development of a novel family of dielectric-plasmonic materials with application extending from light harvesting and photocatalysts to contactless sensors for noninvasive medical diagnostics.

Applications of low-cost sensing technologies for air quality monitoring and exposure assessment: How far have they gone?

Over the past decade, a range of sensor technologies became available on the market, enabling a revolutionary shift in air pollution monitoring and assessment. With their cost of up to three orders of magnitude lower than standard/reference instruments, many avenues for applications have opened up. In particular, broader participation in air quality discussion and utilisation of information on air pollution by communities has become possible. However, many questions have been also asked about the actual benefits of these technologies. To address this issue, we conducted a comprehensive literature search including both the scientific and grey literature. We focused upon two questions: (1) Are these technologies fit for the various purposes envisaged? and (2) How far have these technologies and their applications progressed to provide answers and solutions? Regarding the former, we concluded that there is no clear answer to the question, due to a lack of: sensor/monitor manufacturers' quantitative specifications of performance, consensus regarding recommended end-use and associated minimal performance targets of these technologies, and the ability of the prospective users to formulate the requirements for their applications, or conditions of the intended use. Numerous studies have assessed and reported sensor/monitor performance under a range of specific conditions, and in many cases the performance was concluded to be satisfactory. The specific use cases for sensors/monitors included outdoor in a stationary mode, outdoor in a mobile mode, indoor environments and personal monitoring. Under certain conditions of application, project goals, and monitoring environments, some sensors/monitors were fit for a specific purpose. Based on analysis of 17 large projects, which reached applied outcome stage, and typically conducted by consortia of organizations, we observed that a sizable fraction of them (~ 30%) were commercial and/or crowd-funded. This fact by itself signals a paradigm change in air quality monitoring, which previously had been primarily implemented by government organizations. An additional paradigm-shift indicator is the growing use of machine learning or other advanced data processing approaches to improve sensor/monitor agreement with reference monitors. There is still some way to go in enhancing application of the technologies for source apportionment, which is of particular necessity and urgency in developing countries. Also, there has been somewhat less progress in wide-scale monitoring of personal exposures. However, it can be argued that with a significant future expansion of monitoring networks, including indoor environments, there may be less need for wearable or portable sensors/monitors to assess personal exposure. Traditional personal monitoring would still be valuable where spatial variability of pollutants of interest is at a finer resolution than the monitoring network can resolve.

On-surface synthesis of polyethylenedioxythiophene.

On-surface synthesis of conjugated polymers is made challenging by the need to promote the desired reaction while preventing or minimizing unwanted ancillary reactions that compromise the product integrity. We perform a comprehensive study of the reactions of 2,5-dichloro-3,4-ethylenedioxythiophene on coinage metal surfaces, and demonstrate that only on Ag(111) can we obtain a planar polymer product, polyethylenedioxythiophene (PEDOT).

Quasi free-standing epitaxial graphene fabrication on 3C-SiC/Si(111).

Growing graphene on SiC thin films on Si is a cheaper alternative to the growth on bulk SiC, and for this reason it has been recently intensively investigated. Here we study the effect of hydrogen intercalation on epitaxial graphene obtained by high temperature annealing on 3C-SiC/Si(111) in ultra-high vacuum. By using a combination of core-level photoelectron spectroscopy, low energy electron diffraction, and near-edge x-ray absorption fine structure (NEXAFS) we find that hydrogen saturates the Si atoms at the topmost layer of the substrate, leading to free-standing graphene on 3C-SiC/Si(111). The intercalated hydrogen fully desorbs after heating the sample at 850 °C and the buffer layer appears again, similar to what has been reported for bulk SiC. However, the NEXAFS analysis sheds new light on the effect of hydrogen intercalation, showing an improvement of graphene's flatness after annealing in atomic H at 600 °C. These results provide new insight into free-standing graphene fabrication on SiC/Si thin films.