We demonstrated analog memory, synaptic plasticity, and a spike-timing-dependent plasticity (STDP) function with a nanoscale titanium oxide bilayer resistive switching device with a simple fabrication process and good yield uniformity. We confirmed the multilevel conductance and analog memory characteristics as well as the uniformity and separated states for the accuracy of conductance change. Finally, STDP and a biological triple model were analyzed to demonstrate the potential of titanium oxide bilayer resistive switching device as synapses in neuromorphic devices. By developing a simple resistive switching device that can emulate a synaptic function, the unique characteristics of synapses in the brain, e.g. combined memory and computing in one synapse and adaptation to the outside environment, were successfully demonstrated in a solid state device.
Supercapacitors, based on fast ion transportation, are specialized to provide high power, long stability, and efficient energy storage using highly porous electrode materials. However, their low energy density excludes them from many potential applications that require both high energy density and high power density performances. Using a scalable nanoporous graphene synthesis method involving an annealing process in hydrogen, here we show supercapacitors with highly porous graphene electrodes capable of achieving not only a high power density of 41 kW kg(-1) and a Coulombic efficiency of 97.5%, but also a high energy density of 148.75 Wh kg(-1). A high specific gravimetric and volumetric capacitance (306.03 F g(-1) and 64.27 F cm(-3)) are demonstrated. The devices can retain almost 100% capacitance after 7000 charging/discharging cycles at a current density of 8 A g(-1). The superior performance of supercapacitors is attributed to their ideal pore size, pore uniformity, and good ion accessibility of the synthesized graphene.
Stretchable transparent composites have been synthesized consisting of a silver nanowire (AgNW) network embedded in the surface layer of a crosslinked poly(acrylate) matrix. The interpenetrating networks of AgNWs and the crosslinked polymer matrix lead to high surface conductivity, high transparency, and rubbery elasticity. The presence of carboxylic acid groups on the polymer chains enhances the bonding between AgNWs and the polymer matrix, and further increases the stretchability of the composites. The sheet resistance of the composite electrode increases by only 2.3 times at 50% strain. Repeated stretching to 50% strain and relaxation only causes a small increase of the sheet resistance after 600 cycles. The morphology of the composites during reversible stretching and relaxation has been investigated to expound the conductivity changes.
Defects in three different types of ZnO nanostructures before and after annealing under different conditions were studied. The annealing atmosphere and temperature were found to strongly affect the yellow and orange-red defect emissions, while green emission was not significantly affected by annealing. The defect emissions exhibited a strong dependence on the temperature and excitation wavelength, with some defect emissions observable only at low temperatures and for certain excitation wavelengths. The yellow emission in samples prepared by a hydrothermal method is likely due to the presence of OH groups, instead of the commonly assumed interstitial oxygen defect. The green and orange-red emissions are likely due to donor acceptor transitions involving defect complexes, which likely include zinc vacancy complexes in the case of orange-red emissions.
In this paper, a WSe2 film prepared by chemical vapor deposition (CVD) is transferred onto a tapered fiber, and a WSe2 saturable absorber (SA) is fabricated. In order to measure the third-order optical nonlinearity of the WSe2, the Z-scan technique is applied. The modulation depth of the WSe2 SA is measured as being 21.89%. Taking advantage of the remarkable nonlinear absorption characteristic of the WSe2 SA, a mode-locked erbium-doped fiber laser is demonstrated at 1557.4 nm with a bandwidth of 25.8 nm and signal to noise ratio of 96 dB. To the best of our knowledge, the pulse duration of 163.5 fs is confirmed to be the shortest compared with previous mode-locked fiber lasers based on transition-metal dichalcogenides SAs. These results indicate that WSe2 is a powerful competitor in the application of ultrashort pulse lasers.
In this work graphene sheets grown by chemical vapor deposition (CVD) with controlled numbers of layers were used as transparent electrodes in organic photovoltaic (OPV) devices. It was found that for devices with pristine graphene electrodes, the power conversion efficiency (PCE) is comparable to their counterparts with indium tin oxide (ITO) electrodes. Nevertheless, the chances for failure in OPVs with pristine graphene electrodes are higher than for those with ITO electrodes, due to the surface wetting challenge between the hole-transporting layer and the graphene electrodes. Various alternative routes were investigated and it was found that AuCl3 doping on graphene can alter the graphene surface wetting properties such that a uniform coating of the hole-transporting layer can be achieved and device success rate can be increased. Furthermore, the doping both improves the conductivity and shifts the work function of the graphene electrode, resulting in improved overall PCE performance of the OPV devices. This work brings us one step further toward the future use of graphene transparent electrodes as a replacement for ITO.
We report detailed current-voltage and current-time measurements to reveal the forming and switching behaviors of Cu/Ta2O5/Pt nonvolatile resistive memory devices. The devices can be initially SET (from the OFF state to the ON state) when a low positive bias voltage is applied to the Cu electrode. This first SET operation corresponds to the first formation of a metal filament by inhomogeneous nucleation and subsequent growth of Cu on the Pt electrode, based on the migration of Cu ions in the stable Ta2O5 matrix. After the forming, the device exhibits bipolar switching behavior (SET at positive bias and RESET (from the ON state to the OFF state) at negative bias) with increasing the ON resistance from a few hundred Omega to a few k Omega. From the measurements of the temperature stability of the ON states, we concluded that the RESET process consists of the Joule-heating-assisted oxidation of Cu atoms at the thinnest part of the metal filament followed by diffusion and drift of the Cu ions under their own concentration gradient and the applied electric field, disconnecting the metal filament. With ON resistances of the order of a few k Omega, the SET and RESET operations are repeated by the inhomogeneous nucleation and the Joule-heating-assisted dissolution of a small filament on a remaining filament. This switching model is applicable to the operation of cation-migration-based resistive memories using other oxide materials.
Cotton-based nanocrystalline cellulose (NCC), also known as nanopaper, one of the major sources of renewable materials, is a promising substrate and component for producing low cost fully recyclable flexible paper electronic devices and systems due to its properties (lightweight, stiffness, non-toxicity, transparency, low thermal expansion, gas impermeability and improved mechanical properties). Here, we have demonstrated for the first time a thin transparent nanopaper-based field effect transistor (FET) where NCC is simultaneously used as the substrate and as the gate dielectric layer in an 'interstrate' structure, since the device is built on both sides of the NCC films; while the active channel layer is based on oxide amorphous semiconductors, the gate electrode is based on a transparent conductive oxide. Such hybrid FETs present excellent operating characteristics such as high channel saturation mobility (>7 cm(2) V-1 s(-1)), drain-source current on/off modulation ratio higher than 10(5), enhancement n-type operation and subthreshold gate voltage swing of 2.11 V/decade. The NCC film FET characteristics have been measured in air ambient conditions and present good stability, after two weeks of being processed, without any type of encapsulation or passivation layer. The results obtained are comparable to ones produced for conventional cellulose paper, marking this out as a promising approach for attaining high-performance disposable electronics such as paper displays, smart labels, smart packaging, RFID (radio-frequency identification) and point-of-care systems for self-analysis in bioscience applications, among others.
In this paper, the resistive switching characteristics in a Cu/HfO2:Cu/Pt sandwiched structure is investigated for multilevel non-volatile memory applications. The device shows excellent resistive switching performance, including good endurance, long retention time, fast operation speed and a large storage window (R-OFF/R-ON > 10(7)). Based on the temperature-dependent test results, the formation of Cu conducting filaments is believed to be the reason for the resistance switching from the OFF state to the ON state. By integrating the resistive switching mechanism study and the device fabrication, different resistance values are achieved using different compliance currents in the program process. These resistance values can be easily distinguished in a large temperature range, and can be maintained over 10 years by extrapolating retention data at room temperature. The integrated experiment and mechanism studies set up the foundation for the development of high-performance multilevel RRAM.
The prospect of electronic circuits that are stretchable and bendable promises tantalizing applications such as skin-like electronics, roll-up displays, conformable sensors and actuators, and lightweight solar cells. The preparation of highly conductive and highly extensible materials remains a challenge for mass production applications, such as free-standing films or printable composite inks. Here we present a nanocomposite material consisting of carbon nanotubes, ionic liquid, silver nanoparticles, and polystyrene-polyisoprene-polystyrene having a high electrical conductivity of 3700 S cm 1 that can be stretched to 288% without permanent damage. The material is prepared as a concentrated dispersion suitable for simple processing into free-standing films. For the unstrained state, the measured thermal conductivity for the electronically conducting elastomeric nanoparticle film is relatively high and shows a non-metallic temperature dependence consistent with phonon transport, while the temperature dependence of electrical resistivity is metallic. We connect an electric fan to a DC power supply using the films to demonstrate their utility as an elastomeric electronic interconnect. The huge strain sensitivity and the very low temperature coefficient of resistivity suggest their applicability as strain sensors, including those that operate directly to control motors and other devices.
Photovoltaics and photocatalysis are two significant applications of clean and sustainable solar energy, albeit constrained by their inability to harvest the infrared spectrum of solar radiation. Lanthanide-doped materials are particularly promising in this regard, with tunable absorption in the infrared region and the ability to convert the long-wavelength excitation into shorter-wavelength light output through an upconversion process. In this review, we highlight the emerging applications of lanthanide-doped upconversion materials in the areas of photovoltaics and photocatalysis. We attempt to elucidate the fundamental physical principles that govern the energy conversion by the upconversion materials. In addition, we intend to draw attention to recent technologies in upconversion nanomaterials integrated with photovoltaic and photocatalytic devices. This review also provides a useful guide to materials synthesis and optoelectronic device fabrication based on lanthanide-doped upconversion materials.
Graphene-based nanocomposites have proven to be very promising materials for gas sensing applications. In this paper, we present a general approach for the preparation of graphene-WO3 nanocomposites. Graphene-WO3 nanocomposite thin-layer sensors were prepared by drop coating the dispersed solution onto the alumina substrate. These nanocomposites were used for the detection of NO2 for the first time. TEM micrographs revealed that WO3 nanoparticles were well distributed on graphene nanosheets. Three different compositions (0.2, 0.5 and 0.1 wt%) of graphene with WO3 were used for the gas sensing measurements. It was observed that the sensor response to NO2 increased nearly three times in the case of graphene-WO3 nanocomposite layer as compared to a pure WO3 layer at room temperature. The best response of the graphene-WO3 nanocomposite was obtained at 250 degrees C.
Monolayer MoS2 is a direct band gap semiconductor which has been recently investigated for lowpower field effect transistors. The initial studies have shown promising performance, including a high on/off current ratio and carrier mobility with a high-kappa gate dielectric. However, the performance of these devices strongly depends on the crystalline quality and defect morphology of the monolayers. In order to obtain a detailed understanding of the MoS2 electronic device properties, we examine possible defect structures and their impact on the MoS2 monolayer electronic properties, using density functional theory in combination with scanning tunneling microscopy to identify the nature of the most likely defects. Quantitative understanding based on a detailed knowledge of the atomic and electronic structures will facilitate the search of suitable defect passivation techniques. Our results show that S adatoms are the most energetically favorable type of defect and that S vacancies are energetically more favorable than Mo vacancies. This approach may be extended to other transition-metal dichalcogenides (TMDs), thus providing useful insights to optimize TMD-based electronic devices.
There is a strong interest in the use of biopolymers in the electronic and biomedical industries, mainly towards low-cost applications. The possibility of developing entirely new kinds of products based on cellulose is of current interest, in order to enhance and to add new functionalities to conventional paper-based products. We present our results towards the development of paper-based microfluidics for molecular diagnostic testing. Paper properties were evaluated and compared to nitrocellulose, the most commonly used material in lateral flow and other rapid tests. Focusing on the use of paper as a substrate for microfluidic applications, through an eco-friendly wax-printing technology, we present three main and distinct colorimetric approaches: (i) enzymatic reactions (glucose detection); (ii) immunoassays (antibodies anti-Leishmania detection); (iii) nucleic acid sequence identification (Mycobacterium tuberculosis complex detection). Colorimetric glucose quantification was achieved through enzymatic reactions performed within specific zones of the paper-based device. The colouration achieved increased with growing glucose concentration and was highly homogeneous, covering all the surface of the paper reaction zones in a 3D sensor format. These devices showed a major advantage when compared to the 2D lateral flow glucose sensors, where some carryover of the coloured products usually occurs. The detection of anti-Leishmania antibodies in canine sera was conceptually achieved using a paper-based 96-well enzyme-linked immunosorbent assay format. However, optimization is still needed for this test, regarding the efficiency of the immobilization of antigens on the cellulose fibres. The detection of Mycobacterium tuberculosis nucleic acids integrated with a non-cross-linking gold nanoprobe detection scheme was also achieved in a wax-printed 384-well paper-based microplate, by the hybridization with a species-specific probe. The obtained results with the above-mentioned proof-of-concept sensors are thus promising towards the future development of simple and cost-effective paper-based diagnostic devices.
Metal oxide nanoparticles have marked antibacterial activity. The toxic effect of these nanoparticles, such as those comprised of ZnO, has been found to occur due to an interaction of the nanoparticle surface with water, and to increase with a decrease in particle size. In the present study, we tested the ability of ZnO nanoparticles to affect the viability of the pathogenic yeast, Candida albicans (C. albicans). A concentration-dependent effect of ZnO on the viability of C. albicans was observed. The minimal fungicidal concentration of ZnO was found to be 0.1 mg ml(-1) ZnO; this concentration caused an inhibition of over 95% in the growth of C. albicans. ZnO nanoparticles also inhibited the growth of C. albicans when it was added at the logarithmic phase of growth. Addition of histidine (a quencher of hydroxyl radicals and singlet oxygen) caused reduction in the effect of ZnO on C. albicans depending on its concentration. An almost complete elimination of the antimycotic effect was achieved following addition of 5 mM of histidine. Exciting the ZnO by visible light increased the yeast cell death. The effects of histidine suggest the involvement of reactive oxygen species, including hydroxyl radicals and singlet oxygen, in cell death. In light of the above results it appears that metal oxide nanoparticles may provide a novel family of fungicidal compounds.
Molecular-receptor-targeted imaging of folate receptor positive oral carcinoma cells using folic-acid-conjugated fluorescent Au25 nanoclusters (Au NCs) is reported. Highly fluorescent Au25 clusters were synthesized by controlled reduction of Au+ ions, stabilized in bovine serum albumin (BSA), using a green-chemical reducing agent, ascorbic acid (vitamin-C). For targeted-imaging-based detection of cancer cells, the clusters were conjugated with folic acid (FA) through amide linkage with the BSA shell. The bioconjugated clusters show excellent stability over a wide range of pH from 4 to 14 and fluorescence efficiency of similar to 5.7% at pH 7.4 in phosphate buffer saline (PBS), indicating effective protection of nanoclusters by serum albumin during the bioconjugation reaction and cell-cluster interaction. The nanoclusters were characterized for their physico-chemical properties, toxicity and cancer targeting efficacy in vitro. X-ray photoelectron spectroscopy (XPS) suggests binding energies correlating to metal Au 4f(7/2) similar to 83.97 eV and Au 4f(5/2) similar to 87.768 eV. Transmission electron microscopy and atomic force microscopy revealed the formation of individual nanoclusters of size similar to 1 nm and protein cluster aggregates of size similar to 8 nm. Photoluminescence studies show bright fluorescence with peak maximum at similar to 674 nm with the spectral profile covering the near-infrared (NIR) region, making it possible to image clusters at the 700-800 nm emission window where the tissue absorption of light is minimum. The cell viability and reactive oxygen toxicity studies indicate the non-toxic nature of the Au clusters up to relatively higher concentrations of 500 mu g ml(-1). Receptor-targeted cancer detection using Au clusters is demonstrated on FR+ve oral squamous cell carcinoma (KB) and breast adenocarcinoma cell MCF-7, where the FA-conjugated Au-25 clusters were found internalized in significantly higher concentrations compared to the negative control cell lines. This study demonstrates the potential of using non-toxic fluorescent Au nanoclusters for the targeted imaging of cancer.
Nanoparticles rapidly interact with the proteins present in biological fluids, such as blood. The proteins that are adsorbed onto the surface potentially dictate the biokinetics of the nanomaterials and their fate in vivo. Using nanoparticles with different sizes and surface characteristics, studies have reported the effects of physicochemical properties on the composition of adsorbed plasma proteins. However, to date, few studies have been conducted focusing on the nanoparticles that are commonly exposed to the general public, such as the metal oxides. Using previously established ultracentrifugation approaches, two-dimensional gel electrophoresis and mass spectrometry, the current study investigated the binding of human plasma proteins to commercially available titanium dioxide, silicon dioxide and zinc oxide nanoparticles. We found that, despite these particles having similar surface charges in buffer, they bound different plasma proteins. For TiO2, the shape of the nanoparticles was also an important determinant of protein binding. Agglomeration in water was observed for all of the nanoparticles and both TiO2 and ZnO further agglomerated in biological media. This led to an increase in the amount and number of different proteins bound to these nanoparticles. Proteins with important biological functions were identified, including immunoglobulins, lipoproteins, acute-phase proteins and proteins involved in complement pathways and coagulation. These results provide important insights into which human plasma proteins bind to particular metal oxide nanoparticles. Because protein absorption to nanoparticles may determine their interaction with cells and tissues in vivo, understanding how and why plasma proteins are adsorbed to these particles may be important for understanding their biological responses.
This paper demonstrates that nanospace engineering of KOH activated carbon is possible by controlling the degree of carbon consumption and metallic potassium intercalation into the carbon lattice during the activation process. High specific surface areas, porosities, sub-nanometer (<1 nm) and supra-nanometer (1-5 nm) pore volumes are quantitatively controlled by a combination of KOH concentration and activation temperature. The process typically leads to a bimodal pore size distribution, with a large, approximately constant number of sub-nanometer pores and a variable number of supra-nanometer pores. We show how to control the number of supra-nanometer pores in a manner not achieved previously by chemical activation. The chemical mechanism underlying this control is studied by following the evolution of elemental composition, specific surface area, porosity, and pore size distribution during KOH activation and preceding H3PO4 activation. The oxygen, nitrogen, and hydrogen contents decrease during successive activation steps, creating a nanoporous carbon network with a porosity and surface area controllable for various applications, including gas storage. The formation of tunable sub-nanometer and supra-nanometer pores is validated by sub-critical nitrogen adsorption. Surface functional groups of KOH activated carbon are studied by microscopic infrared spectroscopy.
The interest in nanodiamond applications in biology and medicine is on the rise over recent years. This is due to the unique combination of properties that nanodiamond provides. Small size (similar to 5 nm), low cost, scalable production, negligible toxicity, chemical inertness of diamond core and rich chemistry of nanodiamond surface, as well as bright and robust fluorescence resistant to photobleaching are the distinct parameters that render nanodiamond superior to any other nanomaterial when it comes to biomedical applications. The most exciting recent results have been related to the use of nanodiamonds for drug delivery and diagnostics-two components of a quickly growing area of biomedical research dubbed theranostics. However, nanodiamond offers much more in addition: it can be used to produce biodegradable bone surgery devices, tissue engineering scaffolds, kill drug resistant microbes, help us to fight viruses, and deliver genetic material into cell nucleus. All these exciting opportunities require an in-depth understanding of nanodiamond. This review covers the recent progress as well as general trends in biomedical applications of nanodiamond, and underlines the importance of purification, characterization, and rational modification of this nanomaterial when designing nanodiamond based theranostic platforms.