Table of contents

2D layered SnS₂ nanosheets have attracted increasing research interest due to their highly anisotropic structural, electrical, optical, and mechanical properties. Here, through mechanical exfoliation, few-layer SnS₂ was obtained from as-synthesized many-layered bulk SnS₂. Micro-characterization and Raman study demonstrate the hexagonal symmetry structure of the nanosheets so fabricated. The energy band structures of both SnS₂ bulk and monolayer were investigated comparatively. A highly photosensitive field effect transistor based on the obtained few-layer SnS₂ nanosheets was fabricated, which shows a high I_photo/I_dark ratio of 10³, and keeps the responsivity and external quantum efficiency (EQE) at a realistic level of 8.5 A W⁻¹ and 1.2 × 10³% respectively. This 2D structured high on/off ratio photosensitive field effect device may find promising potential applications in functional electronic/optoelectronic devices or systems.

Hollow spheres have drawn much attention in the area of energy storage and conversion, especially in high-performance supercapacitors owing to their well-defined morphologies, uniform size, low density and large surface area. And quite some significant breakthroughs have been made in advanced supercapacitor electrode materials with hollow sphere structures. In this review, we summarize and discuss the synthesis and application of hollow spheres with controllable structure and morphology as electrode materials for supercapacitors. First, we briefly introduce the fabrication strategies of hollow spheres for electrode materials. Then, we discuss in detail the recent advances in various hollow sphere-based electrode materials for supercapacitors, including single-shelled, yolk-shelled, urchin-like, double-shelled, multi-shelled, and mesoporous hollow structure-based symmetric and asymmetric supercapacitor devices. We conclude this review with some perspectives on the future research and development of the hollow sphere-based electrode materials.

Advanced doping technologies are key for the continued scaling of semiconductor devices and the maintenance of device performance beyond the 14 nm technology node. Due to limitations of conventional ion-beam implantation with thin body and 3D device geometries, techniques which allow precise control over dopant diffusion and concentration, in addition to excellent conformality on 3D device surfaces, are required. Spin-on doping has shown promise as a conventional technique for doping new materials, particularly through application with other dopant methods, but may not be suitable for conformal doping of nanostructures. Additionally, residues remain after most spin-on-doping processes which are often difficult to remove. In situ doping of nanostructures is especially common for bottom-up grown nanostructures but problems associated with concentration gradients and morphology changes are commonly experienced. Monolayer doping has been shown to satisfy the requirements for extended defect-free, conformal and controllable doping on many materials ranging from traditional silicon and germanium devices to emerging replacement materials such as III–V compounds but challenges still remain, especially with regard to metrology and surface chemistry at such small feature sizes. This article summarises and critically assesses developments over the last number of years regarding the application of gas and solution phase techniques to dope silicon-, germanium- and III–V-based materials and nanostructures to obtain shallow diffusion depths coupled with high carrier concentrations and abrupt junctions.

Ultra-sensitive and highly selective detection of glucose is essential for the clinical diagnosis of diabetes. In this paper, an ultra-sensitive glucose sensor was successfully fabricated based on cobalt oxide (Co₃O₄) nanosheets directly grown on nickel foam through a simple hydrothermal method. Characterizations indicated that the Co₃O₄ nanosheets are completely and uniformly wrapped onto the surface of nickel foam to form a three-dimensional heterostructure. The resulting self-standing electrochemical electrode presents a high performance for the non-enzymatic detection of glucose, including short response time (<10 s), ultra-sensitivity (12.97 mA mM⁻¹ cm⁻²), excellent selectivity and low detection limit (0.058 μM, S/N = 3). These results indicate that Co₃O₄ nanosheets wrapped onto nickel foam are a low-cost, practical, and high performance electrochemical electrode for bio sensing.

Control of the work function of molybdenum disulfide (MoS₂) under ultrathin metal was investigated using in situ metal deposition and direct ultraviolet photoelectron spectroscopy measurement in an ultra-high vacuum system. When the metal thickness turned from two dimensional into bulk, the work function was also raised up at the nickel−MoS₂ interface, barely changed at the titanium−MoS₂ interface and lowered at the hafnium−MoS₂ interface. Meanwhile, the mechanisms of charge transfer and band alignment with metal deposition were also discussed. The Schottky barrier at metal−MoS₂ interfaces could be tailored by both types and thicknesses of deposited metal. The low work function metal was a good indicator for MoS₂ contact electrodes. It paved the way towards future high performance MoS₂ device applications.

In the present work, we have studied a nanocomposite of polyaniline nanofiber-graphene microflowers (PANInf-GMF), prepared by an in situ rapid mixing polymerization method. The structural and morphological studies of the nanocomposite (PANInf-GMF) were carried out by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared (FTIR) and Raman spectroscopy. The mesoporous, nanofibrous and microflower structures were observed by scanning electron microscopy. The functional groups and synergetic effects were observed by FTIR and micro-Raman measurements. The water wettability was carried out by a contact angle measurement technique and found to be super hydrophilic in nature towards water. This nanocomposite was deposited onto indium-tin-oxide coated glass substrate by a drop casting method and used for the detection of cholesterol using an electrochemical technique. The differential pulse voltammetry studies show the appreciable increase in the current with the addition of 1.93 to 464.04 mg dl⁻¹ cholesterol concentration. It is also found that the electrodes were highly selective towards cholesterol when compared to other biological interfering analytes, such as glucose, urea, citric acid, cysteine and ascorbic acid. The sensitivity of the sensor is estimated as 0.101 μA mg⁻¹ dl cm⁻² and the lower detection limit as 1.93 mg dl⁻¹. This work will throw light on the preparation of non-enzymatic biosensors based on PANInf-carbon nanostructure composites.

The metal assisted etching mechanism for Si nanowire fabrication, triggered by doping type and level and coupled with choice of metal catalyst, is still very poorly understood. We explain the different etching rates and porosities of wires we observe based on extensive experimental data, using a new empirical model we have developed. We establish as a key parameter, the tunneling through the space charge region (SCR) which is the result of the reduction of the SCR width by level of the Si wafer doping in the presence of the opposite biases of the p- and n-type wafers. This improved understanding should permit the fabrication of high quality wires with predesigned structural characteristics, which hitherto has not been possible.

The development of a thin film with well-defined metallic micro/nanostructures, diverse surface functionalities, and superior electronic/optical properties has been a great challenge to researchers seeking an efficient method for the detection of various analytes in chemical and biological sensing applications. Herein, we report a facile and effective approach to the fabrication of an ordered gold island pattern on a glass substrate with contrasted chemical functionalities, which can provide spatially separated sensing zones for multi-detection. In the proposed method, the combination between the micro/nano-imprint lithography and sequential self-assembly approaches exhibited synergistic effects that allowed well-defined structuring and easy surface functionalization in separated sensing zones. Via imprint lithography, the uniform gold islands/glass structure was successfully fabricated from a readily available gold-coated glass film. In addition, a sequential self-assembling strategy and specific chemical–substrate interactions, such as thiol–gold and silane–glass, enabled the surfaces of gold islands and exposed portions of the glass substrate with contrasting chemical functionalities—SH-functionalized gold islands and NH₂-functionalized glass substrate. A proof-of-concept experiment for the multi-detection of heavy metal ions (Hg²⁺ and Cu²⁺) in an aqueous media was also successfully conducted using the dual-functionalized gold islands/glass structure and surface plasmon resonance measurements. The SH groups on the gold islands and the NH₂ groups on the glass substrate functioned as spatially separated and selective receptors for Hg²⁺ and Cu²⁺ ions, respectively. Therefore, both the detection and quantification of Hg²⁺ and Cu²⁺ ions could be achieved using a single sensing substrate.

Electrochemical reactivity and ionic transport at the nanoscale are essential in many energy applications. In this study, time-resolved Kelvin probe force microscopy (tr-KPFM) is utilized for surface potential mapping of nanostructured ceria, in both space and time domains. The fundamental mechanisms of proton injection and transport are studied as a function of environmental conditions and the presence or absence of triple phase boundaries. Finite element modeling is used to extract physical parameters from the experimental data, allowing not only quantification of the observed processes, but also decoupling of their contributions to the measured signal. The constructed phase diagrams of the parameters demonstrate a thermally activated proton injection reaction at the triple phase boundary, and two transport processes that are responsible for the low-temperature proton conductivity of nanostructured ceria.

Perovskite materials are now an important class of materials in the application areas of photovoltaics and photocatalysis. Inorganic perovskites such as BiFeO₃ (BFO) are promising photocatalyst materials with visible light activity and inherent stability. Here we report the large area sol-gel synthesis of BFO films for solar stimulated water photo oxidation. By modifying the sol-gel synthesis process we have produced a perovskite material that has p-type behaviour and a flat band potential of ∼1.15 V (versus NHE). The photocathode produces a density of −0.004 mA cm⁻² at 0 V versus NHE under AM1.5 G illumination. We further show that 0.6 μmol h⁻¹ of O₂ was produced at an external bias of −0.5 V versus Ag/AgCl. The addition of a non-percolating conducting network of Ag increases the photocurrent to −0.07 mA cm⁻² at 0 V versus NHE (at 2% Ag loading) with an increase to 2.7 μmol h⁻¹ for O₂ production. We attribute the enhancement in photoelectrochemical performance to increased light absorption due light scattering by the incorporated Ag particles, improved charge transfer kinetics at the Ag/BFO interface and reduced over potential losses. We support these claims by an observed shift in flat band and onset potentials after Ag modification through UV–vis spectroscopy, Mott–Schottky plots and j–v curve analysis.

We report a successful approach for the fabrication and characterization of a fiber-optic sensor for ascorbic acid (AA) detection, using a molecularly imprinted polyaniline–Ag (PANI–Ag) nanocomposite layer based on the combined phenomena of surface plasmon resonance (SPR) and localized SPR (LSPR). The PANI–Ag nanocomposite is synthesized by an in situ polymerization process and AA imprints are prepared on the polymeric composite. The confirmation of the PANI–Ag nanocomposite and AA imprinting is performed using various characterization methods such as x-ray diffraction (XRD), UV–vis, Fourier transform infrared spectroscopy and scanning electron microscopy. From XRD, the size of Ag nanoparticles is analyzed. The absorbance spectra are recorded for samples of different concentrations of AA around the sensing region of the probe. An increase in peak absorbance wavelength with the increase in AA concentration is observed with a linear response for the concentration range from 10⁻⁸ M to 10⁻⁶ M. The sensor possesses a high sensitivity of 45.1 nm log⁻¹ M near an AA concentration of 10⁻⁸ M. The limit of detection (LOD) and limit of quantification of the sensor are found to be 7.383 × 10⁻¹¹ M and 4.16 × 10⁻¹⁰ M, respectively. The LOD of the sensor is compared to studies reported in the literature and is found to be the lowest. The sensor possesses several other advantages such as cost effectiveness, selectivity, and low response time (<5 s), along with abilities of remote sensing and online monitoring.

We report the impact of gamma irradiation on the performance of a gold Schottky-contacted ZnO nanorod-based hydrogen sensor. RF-sputtered vertically aligned highly c-axis-oriented ZnO NRs were grown on Si(100) substrate. X-ray diffraction shows no significant change in crystal structure at low gamma doses from 1 to 5 kGy. As gamma irradiation doses increase to 10 kGy, the single crystalline ZnO structure converts to polycrystalline. The photoluminescence spectra also shows suppression of the near-band emission peak and the huge wide-band spectrum indicates the generation of structural defects at high gamma doses. At 1 kGy, the hydrogen sensor response was enhanced from 67% to 77% for 1% hydrogen in pure argon at a 150 °C operating temperature. However, at 10 kGy, the relative response decreases to 33.5%. High gamma irradiation causes displacement damage and defects in ZnO NRs, and as a result, degrades the sensor's performance as a result. Low gamma irradiation doses activate the ZnO NR surface through ionization, which enhances the sensor performance. The relative response of the hydrogen sensor was enhanced by ∼14.9% with respect to pristine ZnO using 1 kGy gamma ray treatment.

Silicon nanowires (SiNWs), fabricated via a top-down approach and then functionalized with biological probes, are used for electrically-based sensing of breast tumor markers. The SiNWs, featuring memristive-like behavior in bare conditions, show, in the presence of biomarkers, modified hysteresis and, more importantly, a voltage memory component, namely a voltage gap. The voltage gap is demonstrated to be a novel and powerful parameter of detection thanks to its high-resolution dependence on charges in proximity of the wire. This unique approach of sensing has never been studied and adopted before. Here, we propose a physical model of the surface electronic transport in Schottky barrier SiNW biosensors, aiming at reproducing and understanding the voltage gap based behavior. The implemented model describes well the experimental I–V characteristics of the device. It also links the modification of the voltage gap to the changing concentration of antigens by showing the decrease of this parameter in response to increasing concentrations of the molecules that are detected with femtomolar resolution in real human samples. Both experiments and simulations highlight the predominant role of the dynamic recombination of the nanowire surface states, with the incoming external charges from bio-species, in the appearance and modification of the voltage gap. Finally, thanks to its compactness, and strict correlation with the physics of the nanodevice, this model can be used to describe and predict the I–V characteristics in other nanostructured devices, for different than antibody-based sensing as well as electronic applications.

We have developed a facile, efficient, low cost and 'green' photochemical approach to preparing surfactant-free Pd nanoparticles and Pd-immobilized@acrylate photo-polymer films at room temperature, under air and without any additional treatment. The reaction system only includes a photo-initiator used as a generator of free radicals and a Pd(II) salt. In ethanol solution, the photochemical reduction of Pd(II) to Pd(0) generates very small metal particles with a narrow size distribution (2–4 nm). Furthermore, we have shown that the formation of Pd nanoparticles from a Pd(II) salt can be reversible thus allowing easy handling and safe storage with the possibility of generating the nanoparticles just before use. In the presence of an acrylate bifunctional monomer, Pd@polymer film was obtained through a 'one-pot, one-step' process resulting from a simultaneous photo-reduction of Pd(II) and photo-polymerization of acrylate units. The simultaneous generation of a 3D polymer network and of metal particles leads to a homogeneous distribution of Pd nanoparticles in the photo-polymer matrix with an average diameter of approximately 3.7 ± 1.1 nm. Such as-prepared Pd@polymer films were found to efficiently catalyze the Mizoroki–Heck reaction in the presence of only 0.9 mequiv. of supported palladium. The major interest of this arrangement is its recoverability and reusability, which makes it very attractive both from a practical and economical viewpoint. Finally, it is worth noting that this innovation offers a great advantage over concurrent methods in that it is simply generated within minutes, it is highly stable, and there is sharp monodispersity in the size of the Pd nanoparticles that can be stored for months without alteration of their physico-chemical properties and catalytic activity.

Luminescent gold nanoclusters (AuNCs) with good biocompatibility have gained much attention in bio-photonics. In addition, they also exhibit a unique photo-physical property, namely thermally activated delayed fluorescence (TADF), by which both singlet and triplet excitons can be harvested. The combination of their non-toxic material property and unique TADF behavior makes AuNCs biocompatible nano-emitters for bio-related light-emitting devices. Unfortunately, the TADF emission is quenched when colloidal AuNCs are transferred to solid states under ambient environment. Here, a facile, low-cost and effective method was used to generate efficient and stable TADF emissions from solid AuNCs under ambient environment using polyvinyl alcohol as a solid matrix. To unravel the underlying mechanism, temperature-dependent static and transient photoluminescence measurements were performed and we found that two factors are crucial for solid TADF emission: small energy splitting between singlet and triplet states and the stabilization of the triplet states. Solid TADF films were also deposited on the flexible plastic substrate with patterned structures, thus mitigating the waveguide-mode losses. In addition, we also demonstrated that warm white light can be generated based on a co-doped single emissive layer, consisting of non-toxic, solution-processed TADF AuNCs and fluorescent carbon dots under UV excitation.

In the current study, the impact of self-synthesized nanoporous titanium oxide (NT) on the morphology, performance and fouling of a polyamide (PA) thin-film composite (TFC) membrane was investigated when the membrane was applied for engineering osmosis (EO). The nanoporous structure and the spindle-like shape of NT were revealed through transmission electron microscopy (TEM), while the AATPS modification of NT was verified by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The results of x-ray photoelectron spectroscopy (XPS) and x-ray diffraction (XRD) confirmed the presence of modified NT (mNT) in the PA dense active layer of the TFC membrane. The outgrowth of the 'leaf-like' structure, upon mNT loading, at the surface of the PA layer was observed by field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). The TFC membrane prepared with 0.05 wt% mNT loading in the organic phase showed the water flux of 26.4 l m⁻² h⁻¹ when tested in the forward osmosis (FO) mode using 0.5M and 10 mM NaCl solution as the draw and feed solution, respectively. Moreover, the TFC-mNT membrane also demonstrated an intensified antifouling property against organic foulant during FO application and it was possible to retrieve the initial water flux almost completely with a simple water-rinsing process.

Upconversion nanoparticles (UCNPs) hold promise as near-infrared light converters to enhance the efficiency of solar cells. However, the prevalent use of UCNPs in solar cells is restricted by their poor electrical conductivity and low emission efficiency. Here reduced graphene oxide (rGO)–NaYF₄:Yb³⁺/Er³⁺ composites are proposed to achieve good electrical conductivity due to the high charge carrier mobility of rGO. Composites of rGO and UCNPs combined by a chemical bond are in situ synthesized by the hydrothermal method, followed by a reduction process. The contact of UCNPs with rGO is proved by SEM, and the binding between the rGO–UCNP composites is confirmed by Fourier transform infrared spectroscopy. The composites are doped into the photoanode of a solar cell. As anticipated, electrochemical impedance spectroscopy confirms the good electrical conductivity of the in situ synthesized rGO–UCNPs. Furthermore, the use of rGO–UCNPs in solar cells enables an enhancement in short-circuit current density and overall efficiency by about 10%. These findings reveal that the combination of UCNPs with rGO opens up new opportunities of extending the use of UCNPs in the area of solar energy harvesting.

A novel, direct method for the characterization of the energy level alignments at bulk-heterojunction (BHJ)/electrode interfaces on the basis of electronic spectroscopy measurements is proposed. The home-made in situ photoemission system is used to perform x-ray/ultraviolet photoemission spectroscopy (XPS/UPS), reflection electron energy loss spectroscopy (REELS) and inverse photoemission spectroscopy of organic-semiconductors (OSCs) deposited onto a Au substrate. Through this analysis system, we are able to obtain the electronic structures of a boron subphthalocyanine chloride:fullerene (SubPC:C₆₀) BHJ and those of the separate OSC/electrode structures (SubPC/Au and C₆₀/Au). Morphology and chemical composition analyses confirm that the original SubPC and C₆₀ electronic structures remain unchanged in the electrodes prepared. Using this technique, we ascertain that the position and area of the nearest peak to the Fermi energy (E_F = 0 eV) in the UPS (REELS) spectra of SubPC:C₆₀ BHJ provide information on the highest occupied molecular orbital level (optical band gap) and combination ratio of the materials, respectively. Thus, extracting the adjusted spectrum from the corresponding SubPC:C60 BHJ UPS (REELS) spectrum reveals its electronic structure, equivalent to that of the C₆₀ materials. This novel analytical approach allows complete energy-level determination for each combination ratio by separating its electronic structure information from the BHJ spectrum.

Resistive random access memory (RRAM) is considered an attractive candidate for next generation memory devices due to its competitive scalability, low-power operation and high switching speed. The technology however, still faces several challenges that overall prohibit its industrial translation, such as low yields, large switching variability and ultimately hard breakdown due to long-term operation or high-voltage biasing. The latter issue is of particular interest, because it ultimately leads to device failure. In this work, we have investigated the physicochemical changes that occur within RRAM devices as a consequence of soft and hard breakdown by combining full-field transmission x-ray microscopy with soft x-ray spectroscopic analysis performed on lamella samples. The high lateral resolution of this technique (down to 25 nm) allows the investigation of localized nanometric areas underneath permanent damage of the metal top electrode. Results show that devices after hard breakdown present discontinuity in the active layer, Pt inclusions and the formation of crystalline phases such as rutile, which indicates that the temperature increased locally up to 1000 K.

By treating oleylamine (OA)-capped Ag–Cu nanoparticles with tetramethylammonium hydroxide (TMAH), we obtained metal nanoparticles that are suspended in polar solvents and sinterable at low temperatures. The simple process with ultra sonication enables synthesis of monodispersed and high purity nanoparticles in an organic base, where the resulting nanoparticles are dispersible in polar solvents such as ethanol and isopropyl alcohol. To investigate the surface characteristics, we conducted Fourier-transform infrared and zeta-potential analyses. After thermal sintering at 200 °C, which is approximately 150 °C lower than the thermal decomposition temperature of OA, an electrically conductive thin film was obtained. Electrical resistivity measurements of the TMAH-treated ink demonstrate that surface modified nanoparticles have a low resistivity of 13.7 × 10⁻⁶ Ω cm. These results confirm the prospects of using low-temperature sinterable nanoparticles as the electrode layer for flexible printed electronics without damaging other stacked polymer layers.

Nickel-rich NiFe thin films (Ni₉₂Fe₈, Ni₈₉Fe₁₁ and Ni₈₃Fe₁₇) were prepared by combining atomic layer deposition (ALD) with a subsequent thermal reduction process. In order to obtain Ni_xFe_1−xO_y films, one ALD supercycle was performed according to the following sequence: m NiCp₂/O₃, with m = 1, 2 or 3, followed by one FeCp₂/O₃ cycle. The supercycle was repeated n times. The thermal reduction process in hydrogen atmosphere was investigated by in situ x-ray diffraction studies as a function of temperature. The metallic nickel iron alloy thin films were investigated and characterized with respect to crystallinity, morphology, resistivity, and magnetism. As proof-of-concept magnetic properties of an array of Ni₈₃Fe₁₇, close to the perfect Permalloy stoichiometry, nanotubes and an isolated tube were investigated.

Hydrogen intercalation in solids is common, complicated, and very difficult to monitor. In a new approach to the problem, we have studied the profile of hydrogen diffusion in single-crystal nanobeams and plates of VO₂, exploiting the fact that hydrogen doping in this material leads to visible darkening near room temperature connected with the metal–insulator transition at 65 °C. We observe hydrogen diffusion along the rutile c-axis but not perpendicular to it, making this a highly one-dimensional diffusion system. We obtain an activated diffusion coefficient, $\sim 0.01\,{{\rm{e}}}^{-0.6\text{eV}/{{k}}_{{\rm{B}}}{T}}\,{{\rm{cm}}}^{2}\,{{\rm{s}}}^{-1},$ applicable in metallic phase. In addition, we observe dramatic supercooling of the hydrogen-induced metallic phase and spontaneous segregation of the hydrogen into stripes implying that the diffusion process is highly nonlinear, even in the absence of defects. Similar complications may occur in hydrogen motion in other materials but are not revealed by conventional measurement techniques.

Highly-ordered and conformal Ni nanotube arrays were prepared by combining atomic layer deposition (ALD) in a porous alumina matrix with a subsequent thermal reduction process. In order to obtain NiO tubes, one ALD NiCp₂/O₃ cycle was repeated 2000 times. After the ALD process, the sample is reduced from NiO to metallic Ni under hydrogen atmosphere. Their magnetic properties such as coercivity and squareness have been determined in a vibrating sample magnetometer in the temperature range from 5–300 K for applied magnetic fields parallel and perpendicular to the nanotube axis. Ni nanotubes synthesized by ALD provide a promising opportunity for potential applications in spintronics, data storage and bio-applications.

Theoretical values of the Hamaker constant have been calculated for metal nanoparticles using Lifshitz theory. The theory describes the Hamaker constant in terms of the permittivity of the interacting bodies. Metal nanoparticles exhibit an internal size effect that alters the dielectric permittivity of the particle when its size falls below the mean free path of the conducting electrons. This size dependence of the permittivity leads to size-dependence of the Hamaker constant for metal nanoparticles. Additionally, the electron damping and the plasma frequency used to model the permittivity of the particle exhibit temperature-dependence, which lead to temperature dependence of the Hamaker constant. In this work, both the size and temperature dependence for gold, silver, copper, and aluminum nanoparticles is demonstrated. The results of this study might be of interest for studying the colloidal stability of nanoparticles in solution.