Intuition-and-Tactile Bimodal Sensing Based on Artificial-Intelligence-Motivated All-Fabric Bionic Electronic Skin for Intelligent Material Perception.

Developing electronic skins (e-skins) with extraordinary perception through bionic strategies has far-reaching significance for the intellectualization of robot skins. Here, an artificial intelligence (AI)-motivated all-fabric bionic (AFB) e-skin is proposed, where the overall structure is inspired by the interlocked bionics of the epidermis-dermis interface inside the skin, while the structural design inspiration of the dielectric layer derives from the branch-needle structure of conifers. More importantly, AFB e-skin achieves intuition sensing in proximity mode and tactile sensing in pressure mode based on the fringing and iontronic effects, respectively, and is simulated and verified through COMSOL finite element analysis. The proposed AFB e-skin in pressure mode exhibits maximum sensitivity of 15.06 kPa-1 (<50 kPa), linear sensitivity of 6.06 kPa-1 (50-200 kPa), and fast response/recovery time of 5.6 ms (40 kPa). By integrating AFB e-skin with AI algorithm, and with the support of material inference mechanisms based on dielectric constant and softness/hardness, an intelligent material perception system capable of recognizing nine materials with indistinguishable surfaces within one proximity-pressure cycle is established, demonstrating abilities that surpass human perception.

Edge-Topological Regulation for in Situ Fabrication of Bridging Nanosensors.

In situ fabrication of well-defined bridging nanostructures is an interesting and unique approach to three-dimensionally design nanosensor structures, which are hardly attainable by other methods. Here, we demonstrate the significant effect of edge-topological regulation on in situ fabrication of ZnO bridging nanosensors. When employing seed layers with a sharp edge, which is a well-defined structure in conventional lithography, the bridging angles and electrical resistances between two opposing electrodes were randomly distributed. The stochastic nature of bridging growth direction at the sharp edges inherently causes such unintentional variation of structural and electrical properties. We propose an edgeless seed layer structure using a two-layers resist method to solve the above uncontrollability of bridging nanosensors. Such bridging nanosensors not only substantially improved the uniformity of structural and electrical properties between two opposing electrodes but also significantly enhanced the sensing responses for NO2 with the smaller variance and the lower limit of detection via in situ controlled electrical contacts.

Role of Seed Layer Crystalline Quality in Photoresponse Performance of Hydrothermally Grown ZnO Nanorods.

We investigated the effects of the crystalline state for seed layers (SLs) on the growth morphology and material characteristics for hydrothermally grown ZnO nanorods (NRs). For this, preheating (PH) at different temperatures (100-300 °C) and O2 plasma treatment (PT) for 9 min were performed during the growth of SLs on p-Si by the aqueous solution-based method to provide the characteristic change on the NR growth platform. An improvement in material properties was achieved from the ZnO NRs grown on the SL crystals of enhanced crystalline quality in terms of the increased preferred orientation (002), the higher UV emission with suppressed deep-level emissions, the recovery of O/Zn stoichiometry, and the reduction of various intrinsic defects. Ultraviolet photodiodes of a p-Si/n-ZnO-NR structure fabricated under the SL conditions of O2 PT and PH at 100 °C showed a significantly enhanced on-off current ratio of ~90 at +5 V and faster photoresponse characteristics presenting a reduction in the fall time from 16 to 9 s.

Synthesis of Monodispersedly Sized ZnO Nanowires from Randomly Sized Seeds.

We demonstrate the facile, rational synthesis of monodispersedly sized zinc oxide (ZnO) nanowires from randomly sized seeds by hydrothermal growth. Uniformly shaped nanowire tips constructed in ammonia-dominated alkaline conditions serve as a foundation for the subsequent formation of the monodisperse nanowires. By precisely controlling the sharp tip formation and the nucleation, our method substantially narrows the distribution of ZnO nanowire diameters from σ = 13.5 nm down to σ = 1.3 nm and controls their diameter by a completely bottom-up method, even initiating from randomly sized seeds. The proposed concept of sharp tip based monodisperse nanowires growth can be applied to the growth of diverse metal oxide nanowires and thus paves the way for bottom-up grown metal oxide nanowires-integrated nanodevices with a reliable performance.

Tailoring the selectivity of titania nanowire arrays grown on titanium fibers by self-assembled modification of trichlorophenylsilane for solid-phase microextraction of polycyclic aromatic hydrocarbons.

The authors describe TiO2 nanowires (TiO2NWs) for solid-phase microextraction of polycyclic aromatic hydrocarbons (PAHs). Well-oriented TiO2NWs were in-situ grown on a titanium wire by a hydrothermal process. The TiO2NWs arrays are radially aligned on the curved titanium fiber substrate. They possess a large surface area and are readily accessible for subsequent self-assembly of trichlorophenylsilane via formation of Ti-O-Si bonds. The TiO2NWs coated fibers show good extraction selectivity for PAHs as shown for phenathrene, fluoranthene, pyrene and benzo[a]pyrene. Following desoption by mobile phases for HPLC analysis, the PAHs were quantified by HPLC with UV detection. The improved extraction capabilities and good selectivity are explained by synergistic hydrophobic and π stacking interactions between the phenyl moieties and the PAHs. Key parameters that affect the extraction performance of the fibers were optimized. The method has a linear response in the 0.1 to 200 µg·L-1 PAH concentration range. Limits of detection (at S/N = 3) range from 20 to 50 ng·L-1. Relative standard deviations (RSDs) for the single fiber repeatability are less than 7.3% (n = 5) and RSDs for the fiber-to-fiber reproducibility are below 8.1% (n = 5). The method was successfully applied to the selective preconcentration and determination of trace PAHs in spiked water samples. Graphical abstract Schematic presentation of fabrication and characterization of the Ti@TiO2NWs@Phenyl fiber. PAHs: polycyclic aromatic hydrocarbons; UVFs: ultraviolet filters; PAEs: phthalate acid esters; CPs: chlorophenols.

Self-Assembled Nanostructured CuCo2 O4 for Electrochemical Energy Storage and the Oxygen Evolution Reaction via Morphology Engineering.

CuCo2 O4 films with different morphologies of either mesoporous nanosheets, cubic, compact-granular, or agglomerated embossing structures are fabricated via a hydrothermal growth technique using various solvents, and their bifunctional activities, electrochemical energy storage and oxygen evolution reaction (OER) for water splitting catalysis in strong alkaline KOH media, are investigated. It is observed that the solvents play an important role in setting the surface morphology and size of the crystallites by controlling nucleation and growth rate. An optimized mesoporous CuCo2 O4 nanosheet electrode shows a high specific capacitance of 1658 F g-1 at 1 A g-1 with excellent restoring capability of ≈99% at 2 A g-1 and superior energy density of 132.64 Wh kg-1 at a power density of 0.72 kW kg-1 . The CuCo2 O4 electrode also exhibits excellent endurance performance with capacity retention of 90% and coulombic efficiency of ≈99% after 5000 charge/discharge cycles. The best OER activity is obtained from the CuCo2 O4 nanosheet sample with the lowest overpotential of ≈290 mV at 20 mA cm-2 and a Tafel slope of 117 mV dec-1 . The superior bifunctional electrochemical activity of the mesoporous CuCo2 O4 nanosheet is a result of electrochemically favorable 2D morphology, which leads to the formation of a very large electrochemically active surface area.

Lattice Transparency of Graphene.

Here, we demonstrated the transparency of graphene to the atomic arrangement of a substrate surface, i.e., the "lattice transparency" of graphene, by using hydrothermally grown ZnO nanorods as a model system. The growth behaviors of ZnO nanocrystals on graphene-coated and uncoated substrates with various crystal structures were investigated. The atomic arrangements of the nucleating ZnO nanocrystals exhibited a close match with those of the respective substrates despite the substrates being bound to the other side of the graphene. By using first-principles calculations based on density functional theory, we confirmed the energetic favorability of the nucleating phase following the atomic arrangement of the substrate even with the graphene layer present in between. In addition to transmitting information about the atomic lattice of the substrate, graphene also protected its surface. This dual role enabled the hydrothermal growth of ZnO nanorods on a Cu substrate, which otherwise dissolved in the reaction conditions when graphene was absent.

Dimensional Tailoring of Hydrothermally Grown Zinc Oxide Nanowire Arrays.

Hydrothermally synthesized ZnO nanowire arrays are critical components in a range of nanostructured semiconductor devices. The device performance is governed by relevant nanowire morphological parameters that cannot be fully controlled during bulk hydrothermal synthesis due to its transient nature. Here, we maintain homeostatic zinc concentration, pH, and temperature by employing continuous flow synthesis and demonstrate independent tailoring of nanowire array dimensions including areal density, length, and diameter on device-relevant length scales. By applying diffusion/reaction-limited analysis, we separate the effect of local diffusive transport from the c-plane surface reaction rate and identify direct incorporation as the c-plane growth mechanism. Our analysis defines guidelines for precise and independent control of the nanowire length and diameter by operating in rate-limiting regimes. We validate its utility by using surface adsorbents that limit reaction rate to obtain spatially uniform vertical growth rates across a patterned substrate.

In situ monitoring of laser-assisted hydrothermal growth of ZnO nanowires: thermally deactivating growth kinetics.

The laser-assisted hydrothermal growth kinetics of a cluster of ZnO nanowires are studied based on optical in situ growth monitoring. The growth yields are orders of magnitude higher than those of conventional hydrothermal methods that use bulk heating. This remarkable improvement is attributed to suppression of precursor depletion occurring by homogeneous growth reactions, as well as to enhanced mass transport. The obtained in situ data show gradually decaying growth kinetics even with negligible precursor consumption. It is revealed that the growth deceleration is caused by thermal deactivation resulting from heat dissipation through the growing nanowires. Finally, it is demonstrated that the tailored temporal modulation of the input power enables sustained growth to extended dimensions. These results provide a key to highly efficient use of growth precursors that has been pursued for industrial use of this functional metal oxide semiconductor.

Single nanowire resistive nano-heater for highly localized thermo-chemical reactions: localized hierarchical heterojunction nanowire growth.

A single nanowire resistive nano-heater (RNH) is fabricated, and it is demonstrated that the RNH can induce highly localized temperature fields, which can trigger highly localized thermo-chemical reactions to grow hierarchical nanowires directly at the desired specific spot such as ZnO nanowire branch growth on a single Ag nanowire.

The Fast and One-Step Growth of ZnO Nanorods on Cellulose Nanofibers for Highly Sensitive Photosensors.

Cellulose is the most abundant organic material on our planet which has a key role in our daily life (e.g., paper, packaging). In recent years, the need for replacing fossil-based materials has expanded the application of cellulose and cellulose derivatives including into electronics and sensing. The combination of nanostructures with cellulose nanofibers (CNFs) is expected to create new opportunities for the development of innovative electronic devices. In this paper, we report on a single-step process for the low temperature (<100 °C), environmentally friendly, and fully scalable CNF-templated highly dense growth of zinc oxide (ZnO) nanorods (NRs). More specifically, the effect of the degree of substitution of the CNF (enzymatic CNFs and carboxymethylated CNFs with two different substitution levels) on the ZnO growth and the application of the developed ZnO NRs/CNF nanocomposites in the development of UV sensors is reported herein. The results of this investigation show that the growth and nature of ZnO NRs are strongly dependent on the charge of the CNFs; high charge promotes nanorod growth whereas with low charge, ZnO isotropic microstructures are created that are not attached to the CNFs. Devices manufactured via screen printing/drop-casting of the ZnO NRs/CNF nanocomposites demonstrate a good photo-sensing response with a very stable UV-induced photocurrent of 25.84 µA. This also exhibits excellent long-term stability with fast ON/OFF switching performance under the irradiance of a UV lamp (15 W).

Sensor-on-Microtips: Design and Development of Hydrothermally Grown ZnO on Micropipette Tips as a Modified Working Electrode for Detection of Glucose.

Miniaturization of electrochemical components has become less common in the last decade, with the focus predominantly being the design and development of state-of-the-art microelectrodes for achieving small volume analysis of samples. However, such microelectrodes involve cumbersome processing procedures to convert the base material for the required application. A potential paradigm shift in such miniaturization could be achieved by using cheaper alternatives such as plastics to build electrochemical components, such as micropipette tips made of polypropylene, which are commercially available at ease. Hence, this work presents the design of an electrochemical working electrode based upon a micropipette tip, involving minimal processing procedures. Furthermore, such a working electrode was realized by sputtering silver onto a bare micropipette tip using a radio-frequency sputtering technique, to obtain electrical contacts on the tip, followed by hydrothermal growth of ZnO, which acted as the active electrode material. The ZnO nanostructures grown on the micropipette tip were characterized for their morphology and surface properties using a scanning electron microscope (SEM), laser microscope, Raman spectrometer, and X-ray photoelectron spectrometer (XPS). The developed micropipette tip-based electrode was then used as the working electrode in a three-electrode system, wherein its electrochemical stability and properties were analyzed using cyclic voltammetry (CV). Furthermore, the above system was used to detect glucose concentrations of 10-200 µM, to evaluate its sensing properties using amperometry. The developed working electrode exhibited a sensitivity of 69.02 µA/µM cm-2 and limit of detection of 67.5 µM, indicating the potential for using such modified micropipette tips as low-cost miniaturized sensors to detect various bio-analytes in sample solutions.

Nitrogen-Doped CuO@CuS Core-Shell Structure for Highly Efficient Catalytic OER Application.

Water electrolysis is a highly efficient route to produce ideally clean H2 fuel with excellent energy conversion efficiency and high gravimetric energy density, without producing carbon traces, unlike steam methane reforming, and it resolves the issues of environmental contamination via replacing the conventional fossil fuel. Particular importance lies in the advancement of highly effective non-precious catalysts for the oxygen evolution reaction (OER). The electrocatalytic activity of an active catalyst mainly depends on the material conductivity, accessible catalytically active sites, and intrinsic OER reaction kinetics, which can be tuned via introducing N heteroatoms in the catalyst structure. Herein, the efficacious nitrogenation of CuS was accomplished, synthesized using a hydrothermal procedure, and characterized for its electrocatalytic activity towards OER. The nitrogen-doped CuO@CuS (N,CuO@CuS) electrocatalyst exhibited superior OER activity compared to pristine CuS (268 and 602 mV), achieving a low overpotential of 240 and 392 mV at a current density of 10 and 100 mA/cm2, respectively, ascribed to the favorable electronic structural modification triggered by nitrogen incorporation. The N,CuO@CuS also exhibits excellent endurance under varied current rates and a static potential response over 25 h with stability measured at 10 and 100 mA/cm2.

Hydrothermal Growth of an Al-Doped α-Ga2O3 Nanorod Array and Its Application in Self-Powered Solar-Blind UV Photodetection Based on a Photoelectrochemical Cell.

Herein, we successfully fabricated an Al-doped α-Ga2O3 nanorod array on FTO using the hydrothermal and post-annealing processes. To the best of our knowledge, it is the first time that an Al-doped α-Ga2O3 nanorod array on FTO has been realized via a much simpler and cheaper way than that based on metal-organic chemical vapor deposition, magnetron sputtering, molecular beam epitaxy, and pulsed laser deposition. And, a self-powered Al-doped α-Ga2O3 nanorod array/FTO photodetector was also realized as a photoanode at 0 V (vs. Ag/AgCl) in a photoelectrochemical (PEC) cell, showing a peak responsivity of 1.46 mA/W at 260 nm. The response speed of the Al-doped device was 0.421 s for rise time, and 0.139 s for decay time under solar-blind UV (260 nm) illumination. Compared with the undoped device, the responsivity of the Al-doped device was ~5.84 times larger, and the response speed was relatively faster. When increasing the biases from 0 V to 1 V, the responsivity, quantum efficiency, and detectivity of the Al-doped device were enhanced from 1.46 mA/W to 2.02 mA/W, from ~0.7% to ~0.96%, and from ~6 × 109 Jones to ~1 × 1010 Jones, respectively, due to the enlarged depletion region. Therefore, Al doping may provide a route to enhance the self-powered photodetection performance of α-Ga2O3 nanorod arrays.

Some Distinct Attributes of ZnO Nanorods Arrays: Effects of Varying Hydrothermal Growth Time.

This study investigates the growth time effect on the structural, morphological, optical, and photoelectrochemical characteristics of highly oriented ZnO nanorod arrays (ZNRAs). The nanorod arrays were grown on ITO substrates using the unified sol-gel spin coating and hydrothermal techniques. ZnO nanoparticles (ZNPs) were synthesized using the sol-gel spin coating method. In contrast, the hydrothermal method was used to grow the ZnO nanorods. The hydrothermal growth time investigated was between 4 and 12 h. The synthesized ZNRAs were used as the photoanode electrodes to investigate their photoelectrochemical (PEC) electrode potency. The as-prepared ZNRAs were characterized using various analytical tools to determine their structures, morphologies, optical, and photoelectrochemical traits. EDX spectra showed the presence of uncontaminated ZnO chemical composition, and FTIR spectra displayed the various functional groups in the samples. A rod-shaped ZnO nanocrystallite with mean lengths and diameters of 300-500 nm and 40-90 nm, respectively, is depicted. HRTEM images indicated the nucleation and growth of ZNRAs with a lattice fringe spacing of 0.26 nm and a growth lattice planer orientation of [002]. The optimum ZNRAs (grown at 8 h) as photoelectrode achieved a photoconversion efficiency of 0.46% and photocurrent density of 0.63 mA/cm2, that was 17 times higher than the one shown by ZNPs with Ag/AgCl as the reference electrode. Both values were higher than those reported in the literature, indicating the prospect of these ZNRAs for photoelectrode applications.

Low-Temperature Hydrothermal Growth of ZnO Nanowires on AZO Substrates for FACsPb(IBr)3 Perovskite Solar Cells.

Electron and hole transport layers (ETL and HTL) play an essential role in shaping the photovoltaic performance of perovskite solar cells. While compact metal oxide ETL have been largely explored in planar n-i-p device architectures, aligned nanowires or nanorods remain highly relevant for efficient charge extraction and directional transport. In this study, we have systematically grown ZnO nanowires (ZnO NWs) over aluminum-doped zinc oxide (AZO) substrates using a low-temperature method, hydrothermal growth (HTG). The main growth parameters were varied, such as hydrothermal precursors concentrations (zinc nitrate hexahydrate, hexamethylenetetramine, polyethylenimine) and growing time, in order to finely control NW properties (length, diameter, density, and void fraction). The results show that ZnO NWs grown on AZO substrates offer highly dense, well-aligned nanowires of high crystallinity compared to conventional substrates such as FTO, while demonstrating efficient FACsPb(IBr)3 perovskite device performance, without the requirement of conventional compact hole blocking layers. The device performances are discussed based on NW properties, including void fraction and aspect ratio (NW length over diameter). Finally, AZO/ZnO NW-based devices were fabricated with a recent HTL material based on a carbazole moiety (Cz-Pyr) and compared to the spiro-OMeTAD reference. Our study shows that the Cz-Pyr-based device provides similar performance to that of spiro-OMeTAD while demonstrating a promising stability in ambient conditions and under continuous illumination, as revealed by a preliminary aging test.

Fabrication of Isomorphously Substituted W-MFI Membrane with High Performance for Ethanol Separation from Water.

Isomorphous substitution of heteroatoms is an effective platform for finely tuning the pore chemistry, pore structure, and surface properties of the zeolite framework as catalysts or separation membranes. A continuous and compact isomorphously substituted tungsten (W)-MFI membrane was firstly developed on coarse α-Al2 O3 tube dip-coated with W-MFI seeds using hydrothermal secondary growth and pretreated synthesis solution. The synthesized W-MFI membrane is found to be ethanol permselective having a pervaporation based separation factor and flux of 69 and 2.50 kg/m2 h, respectively while exhibiting the highest separation index of 170 kg/m2 h for the separation of 5 wt% ethanol-water mixture among the reported heteroatoms substituted and α-Al2 O3 supported tubular MFI membranes. The isomorphous substitution of W improves the hydrophobicity and also plays a significant role for the enhanced separation performance.

Enhanced Output Performance of a Flexible Piezoelectric Nanogenerator Realized by Lithium-Doped Zinc Oxide Nanowires Decorated on MXene.

A flexible piezoelectric composite is composed of a polymer matrix and piezoelectric ceramic fillers to achieve good mechanical flexibility and processability. The overall piezoelectric performance of a composite is largely determined by the piezoelectric filler inside. Thus, different dispersion methods and additives that can promote the dispersion of piezoelectric ceramics and optimal composite structures have been actively investigated. However, relatively few attempts have been made to develop a filler that can effectively contribute to the performance enhancement of piezoelectric devices. In the present work, we introduce the fabrication and performance of the composite piezoelectric devices composed of Li-doped ZnO nanowires (Li: ZnO NWs) grown on the surface of MXene (Ti3C2) via the hydrothermal process. Through this approach, a semiconductor-metal hybrid structure is formed, increasing the overall permittivity. Moreover, the Ti3C2 layer can serve as a local ground in the composite so that the ferroelectric phase-transformed Li: ZnO NWs grown on its surface can be more effectively polarized during the poling process. In addition, the NW-covered surface of Ti3C2 prevents the aggregation of metallic Ti3C2 particles, promoting a more uniform electric field distribution during the poling process. As a result, the output performance of the piezoelectric nanogenerator (PENG) fabricated with a Li: ZnO NW/Ti3C2 composite was greatly improved compared to that of the devices fabricated with Li: ZnO NWs without the Ti3C2 platform. Specifically, the Li: ZnO NW/Ti3C2 composite piezoelectric nanogenerator (PENG) demonstrated a twofold higher output power density (∼9 µW/cm2) compared with the values obtained from the PENG devices based on Li: ZnO NWs. The approach introduced in this work can be easily adopted for an effective ferroelectric filler design to improve the output performance of the piezoelectric composite.

Single-Mode Microwave Heating-Induced Concurrent Out-of-Plane Twin Growth Suppression and In-Plane Epitaxial Growth Promotion of b-Oriented MFI Film under Mild Reaction Conditions.

In this study, single-mode microwave heating was applied in epitaxial growth of b-oriented MFI seed monolayer prepared by facile manual assembly, resulting in the formation of well-intergrown and highly b-oriented MFI film with few twins. It exhibited a precise molecular sieving property at a reaction temperature no higher than 100 °C within 2 hours, therefore making it possible for easy operation in an open environment. The capability for concurrent suppression of undesired out-of-plane twin growth and promotion of in-plane epitaxial growth rate under mild reaction conditions was attributed to the obvious superiority of single-mode microwave heating in comparison with conventional multi-mode microwave heating in aspects of microwave field uniformity and intensity. Our research indicated that the single-mode microwave heating technique could potentially be a useful tool for improving the microstructure and therefore the performance of diverse zeolite films.

Atomic Layer Deposition Seeded Growth of Rutile SnO2 Nanowires on Versatile Conducting Substrates.

Extended and oriented rutile nanowires (NWs) hold great promise for numerous applications because of their various tunable physicochemical properties in air and/or solution media, but their direct synthesis on a wide range of conducting substrates remains a significant challenge. Their device performance is governed by relevant NW geometries that cannot be fully controlled to date by varying bulk synthetic conditions. Herein, orientation engineering of rutile SnO2 NWs on a variety of conducting substrates by atomic layer deposition (ALD) seeding has been investigated. The seeded growth controls the nucleation event of the NW, and thicknesses and crystallographic properties of seed layers are the key parameters toward tuning the NW characteristics. The seed layers on carbon cloth produce NWs with highly enhanced electrochemically active surface area, which would show efficient electrochemical CO2 reduction. In addition, the hierarchical architecture resulted from the seeded growth of NWs on SnO2 nanosheets allows thin layers of BiVO4, forming a heterojunction photoanode, which shows a record charge separation efficiency of 96.6% and a charge-transfer efficiency of 90.2% at 1.23 V versus the reversible hydrogen electrode among, to date, the reported BiVO4-based photoanodes for water oxidation. Our study illustrates that such a versatile interfacial engineering effort by the ALD technique would be promising for further wide range of practical applications.