Organo-metal halide perovskite field-effect transistors present serious challenges in terms of device stability and hysteresis in the current-voltage characteristics. Migration of ions located at grain boundaries and surface defects in the perovskite film are the main reasons for instability and hysteresis issues. Here, we introduce a perovskite grain molecular cross-linking approach combined with amine-based surface passivation to address these issues. Molecular cross-linking was achieved through hydrogen bond interactions between perovskite halogens and dangling bonds present at grain boundaries and a hydrophobic cross-linker, namely diethyl-(12-phosphonododecyl)phosphonate, added to the precursor solution. With our approach, we obtained smooth and compact perovskite layers composed of tightly bound grains hence significantly suppressing the generation and migration of ions. Moreover, we achieved efficient surface passivation of the perovskite films upon surface treatment with an amine-bearing polymer, namely polyethylenimine ethoxylated. With our synergistic grain and surface passivation approach, we were able to demonstrate the first perovskite transistor with a complete lack of hysteresis and unprecedented stability upon continuous operation under ambient conditions. Added to the merits are its ambipolar transport of opposite carriers with balanced hole and electron mobilities of 4.02 and 3.35 cm2 V-1 s-1, respectively, its high Ion/Ioff ratio >104 and the lowest sub-threshold swing of 267 mV dec-1 reported to date for any perovskite transistor. These remarkable achievements obtained through a cost-effective molecular cross-linking of grains combined with amine-based surface passivation of the perovskite films open a new era and pave the way for the practical application of perovskite transistors in low-cost electronic circuits.
In recent assassinations reported in London and Malaysia, nerve agents were used to cause death, by skin poisoning. Skin decontamination is the ultimate and most important defense against nerve agent poisoning, because no effective antidote currently exists. However, almost no existing material can achieve effective and rapid decontamination without irritating the skin. This study links proteins that exhibit no decontamination ability with polymers to form a nanocomposite. This creates a nanospace on the surface of the protein that attracts and traps organic molecules, effectively adsorbing the nerve agent Soman within several seconds, without irritating the skin. Analysis of the different components of proteins and polymers reveals that the decontamination efficiency is considerably affected by the thickness of the coated polymer. Moreover, the thickness of the layer is predominantly determined by the size and species of the core and the crosslinking method. Further in vivo experiments on rats poisoned with Soman verify the efficiency and safety of the nanocomposite. These results could be used to design and synthesize more multi-functional and effective decontamination materials.
We exploit the possibility of enhancing the molecular transport of liquids through graphene films using amplitude modulated surface acoustic waves (SAWs) to demonstrate effective and efficient nanoparticle filtration. The use of the SAW, which is an extremely efficient means for driving microfluidic transport, overcomes the need for the large mechanical pumps required to circumvent the large pressure drops encountered in conventional membranes for nanoparticle filtration. 100% filtration efficiency was obtained for micron-dimension particulates, decreasing to only 95% for the filtration of particles of tens of nanometers in dimension, which is comparable to that achieved with other methods. To circumvent clogging of the film, which is typical with all membrane filters, a backwash operation to flush the nanoparticles is incorporated simply by reversing the SAW-induced flow such that 98% recovery of the initial filtration rate is recovered. Given these efficiencies, together with the low cost and compact size of the chipscale SAW devices, we envisage the possibility of scaling out the process by operating a large number of devices in parallel to achieve typical industrial-scale throughputs with potential benefits in terms of substantially lower capital, operating and maintenance costs.
The present work reports a detailed mechanistic interpretation of the role of the solubility of dopants and resultant midgap defect energies in band gap engineering. While there is a general perception that a single dopant is associated with single solubility and defect mechanisms, in reality, the potential for multiple solubility and defect mechanisms requires a more nuanced interpretation. Similarly, Kröger-Vink defect equilibria assume that stoichiometries during substitutional and interstitial solid solubility as well as Schottky and Frenkel pair formation are compensated by the diffusion of matrix ions to the grain boundaries or surface. However, this approach does not allow the possibility that stoichiometry is uncompensated, where diffusion of the matrix ion to lattice interstices occurs, followed by charge compensation by redox of this ion. Consequently, a modified defect equilibria formalism has been developed in order to allow description of this situation. Experimental data for the structural, chemical, semiconducting, and photocatalytic properties as a function of doping level are correlated with conceptual structural models, a comprehensive energy band diagram, and the corresponding defect equilibria. These correlations reveal the complex mechanisms of the interrelated solubility and defect formation mechanisms, which change significantly and irregularly as a function of small changes in doping level. The analyses confirm that the assumption of single mechanisms of solid solubility and defect formation may be simplifications of more complex processes. The generation of (1) a matrix of complementary characterisation and analytical data, (2) the calculation of a complete energy band diagram, (3) consideration of charge compensation mechanisms and redox beyond the limitations of Kröger-Vink approaches, and (4) the development of models of corresponding structural analogies combine to create a new approach to interpret and explain experimental data. These strategies allow deconstruction of these complex issues and thus targeting of optimal and possibly unique doping levels to achieve lattice configurations that may be energetically and structurally unfavorable. These approaches then can be applied to other doped semiconducting systems.
Due to the complexity of surgery for large-area bone injuries, implanting a large volume of materials into the injury site remains a big challenge in orthopedics. To solve this difficulty, in this study, a series of biomimetic hydroxyapatite/shape-memory composite scaffolds were designed and synthesized with programmable pore structures, based on poly(ε-caprolactone) (PCL), polytetrahydrofuran (PTMG) and the osteoconductive hydroxyapatite (HA). The obtained scaffolds presented various pore structures, high connectivity, tunable mechanical properties, and excellent shape memory performance. Moreover, the mineralization activity of the developed scaffolds could enhance the formation of hydroxyapatite and they showed good biocompatibility in vitro. The in vivo experiments show that scaffolds could promote the formation of new bone in critical size cranial defects. The programmable porous scaffold biomaterials exhibited potential application promise in bone regeneration.
Developing a meta-structure with near-unity absorbance in the visible and infrared spectra for solar energy harvesting, photodetection, thermal imaging, photo-trapping, and optical communications is a long-term research challenge. This research presents a four-layered (insulator-metal-insulator-metal) meta-structure unit cell that showed a peak absorbance of 99.99% at 288-300 nm and the average absorbance of 99.18% over the 250-2000 nm wavelength range in TE and TM modes, respectively. The symmetric pattern of the resonator layer shows polarization insensitivity with an average absorption of 99.18% in both TE and TM modes. Furthermore, the proposed design shows a wide incident angle stability up to ≤60 degrees in both TE and TM modes. The proposed structure also exhibits negative index properties at 288-300 nm and 1000-2000 nm, respectively. The negative index properties of the proposed design generate an anti-parallel surface current flow in the ground and resonator layers, which induces magnetic and electric field resonance and increases absorption. The performance of the proposed design is further validated by the interference theory model and a zero value for the polarization conversion ratio (PCR). The electric field E, magnetic field H, and current distribution are analyzed to explain the absorption mechanism of the proposed meta-structure unit cell. It also exhibits the highest photo-thermal conversion efficiency of 99.11%, demonstrating the viability of the proposed design as a solar absorber. The proposed design promises potentially valuable applications such as solar energy harvesting, photodetection, thermal imaging, photo-trapping, and optical communications because of its decent performance.
The search for effective and non-invasive delivery modules to transport therapeutic molecules across skin has led to the discovery of a number of nanocarriers (viz.: liposomes, ethosomes, dendrimers, etc.) in the last few decades. However, available literature suggests that these delivery modules face several issues including poor stability, low encapsulation efficiency, and scale-up hurdles. Recently, carbon nanotubes (CNTs) emerged as a versatile tool to deliver therapeutics across skin. Superior stability, high loading capacity, well-developed synthesis protocol as well as ease of scale-up are some of the reason for growing interest in CNTs. CNTs have a unique physical architecture and a large surface area with unique surface chemistry that can be tailored for vivid biomedical applications. CNTs have been thus largely engaged in the development of transdermal systems such as tuneable hydrogels, programmable nonporous membranes, electroresponsive skin modalities, protein channel mimetic platforms, reverse iontophoresis, microneedles, and dermal buckypapers. In addition, CNTs were also employed in the development of RNA interference (RNAi) based therapeutics for correcting defective dermal genes. This review expounds the state-of-art synthesis methodologies, skin penetration mechanism, drug liberation profile, loading potential, characterization techniques, and transdermal applications along with a summary on patent/regulatory status and future scope of CNT based skin therapeutics.
An integrated cohesive band structure of carbon nanotubes (CNTs) applicable to all chirality directions (n, m), starting from the Dirac cone of a graphene nanolayer in k-space, is demarcated, in direct contrast to dissimilar chiral and achiral versions in the published literature. The electron wave state of a CNT is quantized into one-dimensional (1-D) nanostructure with a wrapping mode, satisfying the boundary conditions from one Dirac K-point to an equivalent neighboring one with an identical phase and returning to the same K point. The repetitive rotation for an identical configuration with added band index (n-m)mod3, yields one metallic (M) with zero bandgap corresponding to (n-m)mod3 = 0, semiconducting state SC1 with (n-m)mod3 = 1 and SC2 with (n-m)mod3 = 2. The band gap and effective mass of SC2 state are twice as large as those of SC1 state. A broad-spectrum expression signifying the linear dependence of the effective mass on the bandgap is obtained. Both the Fermi energy and the intrinsic velocity limiting the current to the saturation level is calculated as a function of the carrier concentration. Limitations of the parabolic approximation are pointed out. Several new features of the band structure are acquired in a seamlessly unified mode for all CNTs, making it suitable for all-encompassing applications. Applications of the theory to high-field transport are advocated with an example of a metallic CNT, in agreement with experimental observations. The mechanism behind the breakdown of the linear current-voltage relation of Ohm's law and the associated surge in resistance are explained on the basis of the nonequilibrium Arora's distribution function (NEADF). These results are important for the performance evaluation and characterization of a variety of applications on CNT in modern nanoscale circuits and devices.
The design of DNA nanotubes is a promising and hot research branch in structural DNA nanotechnology, which is rapidly developing as a versatile method for achieving subtle nanometer scale materials and molecular diagnostic/curative devices. Multifarious methods have been proposed to achieve varied DNA nanotubes, such as using square tiles and single-stranded tiles, but it is still a challenge to develop a bottom-up assembly way to build DNA nanotubes with different diameters and patterns using certain universal DNA nanostructures. This work addresses the challenge by assembling three types of spatial DNA nanotubes with different diameters and patterns from the so-called "basic bricks", i.e., hierarchical DNA sub-tiles. A high processing rate and throughput synthesis of DNA nanotubes are observed and analyzed by atomic force microscopy. Experimental observations and data analysis suggests the stability and controllability of DNA nanotubes assembled by hierarchical DNA sub-tiles.
12 years after the introduction of DNA-templated silver nanoclusters (DNA-AgNCs), exciting progress has been made and yet we are still in the midst of trying to fully understand this nanomaterial. The prominent excellence of DNA-AgNCs is undoubtedly its modulatable emission property, of which how variation in DNA templates causes emission tuning remains elusive. Based on the up-to-date DNA-AgNCs, we aim to establish the correlation between the structure/sequence of DNA templates and emission behaviour of AgNCs. Herein, we systematically present a wide-range of DNA-AgNCs based on the structural complexity of the DNA templates, including single-stranded DNA (ssDNA), double-stranded DNA (dsDNA), triple-stranded DNA (tsDNA) and DNA nanostructures. For each DNA category, we discuss the emission property, quantum yield and synthesis condition of the respective AgNCs, before cross-comparing the impact of different DNA scaffolds on the properties of AgNCs. A future outlook for this area is given as a conclusion. By putting the information together, this review may shed new light on understanding DNA-AgNCs while we are expecting continuous breakthroughs in this field.
Metal-free carbonaceous nanomaterials have witnessed a renaissance of interest due to the surge in the realm of nanotechnology. Among myriads of carbon-based nanostructures with versatile dimensionality, one-dimensional (1D) carbon nanotubes (CNTs) and zero-dimensional (0D) carbon dots (CDs) have grown into a research frontier in the past few decades. With extraordinary mechanical, thermal, electrical and optical properties, CNTs are utilized in transparent displays, quantum wires, field emission transistors, aerospace materials, etc. Although CNTs possess diverse characteristics, their most attractive property is their unique photoluminescence. On the other hand, another growing family of carbonaceous nanomaterials, which is CDs, has drawn much research attention due to its cost-effectiveness, low toxicity, environmental friendliness, fluorescence, luminescence and simplicity to be synthesized and functionalized with surface passivation. Benefiting from these unprecedented properties, CDs have been widely employed in biosensing, bioimaging, nanomedicine, and catalysis. Herein, we have systematically presented the fascinating properties, preparation methods and multitudinous applications of CNTs and CDs (including graphene quantum dots). We will discuss how CNTs and CDs have emerged as auspicious nanomaterials for potential applications, especially in electronics, sensors, bioimaging, wearable devices, batteries, supercapacitors, catalysis and light-emitting diodes (LEDs). Last but not least, this review is concluded with a summary, outlook and invigorating perspectives for future research horizons in this emerging platform of carbonaceous nanomaterials.
Green synthesis approaches are gaining significance as promising routes for the sustainable preparation of nanoparticles, offering reduced toxicity towards living organisms and the environment. Nanomaterials produced by green synthesis approaches can offer additional benefits, including reduced energy inputs and lower production costs than traditional synthesis, which bodes well for commercial-scale production. The biomolecules and phytochemicals extracted from microbes and plants, respectively, are active compounds that function as reducing and stabilizing agents for the green synthesis of nanoparticles. Microorganisms, such as bacteria, yeasts, fungi, and algae, have been used in nanomaterials' biological synthesis for some time. Furthermore, the use of plants or plant extracts for metal and metal-based hybrid nanoparticle synthesis represents a novel green synthesis approach that has attracted significant research interest. This review discusses various biosynthesis approaches via microbes and plants for the green preparation of metal and metal oxide nanoparticles and provides insights into the molecular aspects of the synthesis mechanisms and biomedical applications. The use of agriculture waste as a potential bioresource for nanoparticle synthesis and biomedical applications of biosynthesized nanoparticles is also discussed.
As an indispensable energy source, ammonia plays an essential role in agriculture and various industries. Given that the current ammonia production is still dominated by the energy-intensive and high carbon footprint Haber-Bosch process, photocatalytic nitrogen fixation represents a low-energy consuming and sustainable approach to generate ammonia. Heterostructured photocatalysts are hybrid materials composed of semiconductor materials containing interfaces that make full use of the unique superiorities of the constituents and synergistic effects between them. These promising photocatalysts have superior performances and substantial potential in photocatalytic reduction of nitrogen. In this review, a wide spectrum of recently developed heterostructured photocatalysts for nitrogen fixation to ammonia are evaluated. The fundamentals of solar-to-ammonia conversion, basic principles of various heterojunction photocatalysts and modification strategies are systematically reviewed. Finally, a brief summary and perspectives on the ongoing challenges and directions for future development of nitrogen photofixation catalysts are also provided.
Liquid-exfoliated 2D transition metal disulfides (TMDs) are potential substitutes for poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as hole transport layers (HTLs) in Organic Solar Cells (OSCs). Herein, high-yield and high-quality WS2 flake layers are prepared by comprehensively controlling the initial concentration, sonication processing time and centrifugal speed. The WS2 layers deposited on in situ transparent indium tin oxide (ITO) without plasma treatment show higher uniformity and conductivity than that formed on ITO after plasma treatment. With a significant increase in the short-circuit current density (JSC), the power conversion efficiency (PCE) of PM6:Y6-based non-fullerene OSCs using optimized WS2 as the HTL is higher than that using PEDOT:PSS as the HTL(15.75% vs. 15.31%). Combining the morphology characteristics with carrier recombination characteristics, the higher quality of the ITO/WS2 composite substrate leads to better charge transport and a lower bimolecular recombination rate in OSCs, thereby improving the device performance.
Titanium dioxide (TiO2) is one of the most widely investigated metal oxides due to its extraordinary surface, electronic and catalytic properties. However, the large band gap of TiO2 and massive recombination of photogenerated electron-hole pairs limit its photocatalytic and photovoltaic efficiency. Therefore, increasing research attention is now being directed towards engineering the surface structure of TiO2 at the most fundamental and atomic level namely morphological control of {001} facets in the range of microscale and nanoscale to fine-tune its physicochemical properties, which could ultimately lead to the optimization of its selectivity and reactivity. The synthesis of {001}-faceted TiO2 is currently one of the most active interdisciplinary research areas and demonstrations of catalytic enhancement are abundant. Modifications such as metal and non-metal doping have also been extensively studied to extend its band gap to the visible light region. This steady progress has demonstrated that TiO2-based composites with {001} facets are playing and will continue to play an indispensable role in the environmental remediation and in the search for clean and renewable energy technologies. This review encompasses the state-of-the-art research activities and latest advancements in the design of highly reactive {001} facet-dominated TiO2via various strategies, including hydrothermal/solvothermal, high temperature gas phase reactions and non-hydrolytic alcoholysis methods. The stabilization of {001} facets using fluorine-containing species and fluorine-free capping agents is also critically discussed in this review. To overcome the large band gap of TiO2 and rapid recombination of photogenerated charge carriers, modifications are carried out to manipulate its electronic band structure, including transition metal doping, noble metal doping, non-metal doping and incorporating graphene as a two-dimensional (2D) catalyst support. The advancements made in these aspects are thoroughly examined, with additional insights related to the charge transfer events for each strategy of the modified-TiO2 composites. Finally, we offer a summary and some invigorating perspectives on the major challenges and new research directions for future exploitation in this emerging frontier, which we hope will advance us to rationally harness the outstanding structural and electronic properties of {001} facets for various environmental and energy-related applications.
Quasi-homogeneous ligand-protected gold nanoclusters (Au NCs) with atomic precision and well-defined structure offer great opportunity for exploring the catalytic nature of nanogold catalysts at a molecular level. Herein, using real-time electrospray ionization mass spectrometry (ESI-MS), we have successfully identified the desorption and re-adsorption of p-mercaptobenzoic acid (p-MBA) ligands from Au25(p-MBA)18 NC catalysts during the hydrogenation of 4-nitrophenol in solution. This ligand dynamic (desorption and re-adsorption) would initiate structural transformation of Au25(p-MBA)18 NC catalysts during the reaction, forming a mixture of smaller Au NCs (Au23(p-MBA)16 as the major species) at the beginning of catalytic reaction, which could further be transformed into larger Au NCs (Au26(p-MBA)19 as the major species). The adsorption of hydrides (from NaBH4) is identified as the determining factor that could induce the ligand dynamic and structural transformation of NC catalysts. This study provides fundamental insights into the catalytic nature of Au NCs, including catalytic mechanism, active species and stability of Au NC catalysts during a catalytic reaction.
The usability and tunability of the essential InP-InGaAs material combination in nanowire-based quantum wells (QWs) are assessed. The wurtzite phase core-multi-shell InP-InGaAs-InP nanowire QWs are characterised using cross-section transmission electron microscopy and photoluminescence measurements. The InP-InGaAs direct interface is found to be sharp while the InGaAs-InP inverted interface is more diffused, in agreement with their planar counterpart. Bright emission is observed from the single nanowires containing the QWs at room temperature, with no emission from the InP core or outer barrier. The tunability of the QW emission wavelength in the 1.3-1.55 μm communication wavelength range is demonstrated by varying the QW thickness and in the 1.3 μm range by varying the composition. The experiments are supported by simulation of the emission wavelength of the wurtzite phase InP-InGaAs QWs in the thickness range considered. The radial heterostructure is further extended to design multiple QWs with bright emission, therefore establishing the capability of this material system for nanowire based optical devices for communication applications.
Neurodegenerative disorder is an illness involving neural dysfunction/death attributed to complex pathological processes, which eventually lead to the mortality of the host. It is generally recognized through features such as mitochondrial dysfunction, protein aggregation, oxidative stress, metal ions dyshomeostasis, membrane potential change, neuroinflammation and neurotransmitter impairment. The aforementioned neuronal dysregulations result in the formation of a complex neurodegenerative microenvironment (NME), and may interact with each other, hindering the performance of therapeutics for neurodegenerative disease (ND). Recently, smart nanoassemblies prepared from functional nanoparticles, which possess the ability to interfere with different NME factors, have shown great promise to enhance the diagnostic and therapeutic efficacy of NDs. Herein, this review highlights the recent advances of stimuli-responsive nanoassemblies that can effectively combat the NME for the management of ND. The first section outlined the NME properties and their interrelations that are exploitable for nanoscale targeting. The discussion is then extended to the controlled assembly of functional nanoparticles for the construction of stimuli-responsive nanoassemblies. Further, the applications of stimuli-responsive nanoassemblies for the enhanced diagnosis and therapy of ND are introduced. Finally, perspectives on the future development of NME-tailored nanomedicines are given.
Solution processed zirconium acetylacetonate (Zr(acac)) is successfully employed as an electron extraction layer, replacing conventional titanium oxide, in planar CH3NH3PbI3 perovskite solar cells. The as-prepared Zr(acac) film possesses high transparency, high conductivity, a smooth morphology, high wettability, compatibility with PbI2 DMF solution, and an energy level matching that of CH3NH3PbI3 perovskite material. An average power conversion efficiency of about 11.93%, along with a high fill factor of 74.36%, an open circuit voltage of 1.03 V, and a short-circuit current density of 15.58 mA cm(-2) is achieved. The overall performance of the devices is slight better than that of cells using ruthenium acetylacetonate (Ru(acac)). The differences between solar cells with different electron extraction layers in charge recombination, charge transport and transfer and lifetime are further explored and it is demonstrate that Zr(acac) is a more effective and promising electron extraction layer. This work provides a simple, and cost effective route for the preparation of an effective hole extraction layer.