Self-Competitive Growth of CsPbBr3 Planar Nanowire Array.

Semiconductor planar nanowire arrays (PNAs) are essential for achieving large-scale device integration. Direct heteroepitaxy of PNAs on a flat substrate is constrained by the mismatch in crystalline symmetry and lattice parameters between the substrate and epitaxial nanowires. This study presents a novel approach termed "self-competitive growth" for heteroepitaxy of CsPbBr3 PNAs on mica. The key to inducing the self-competitive growth of CsPbBr3 PNAs on mica involves restricting the nucleation of CsPbBr3 nanowires in a high-adsorption region, which is accomplished by overlaying graphite sheets on the mica surface. Theoretical calculations and experimental results demonstrate that CsPbBr3 nanowires oriented perpendicular to the boundary of the high-adsorption area exhibit greater competitiveness in intercepting the growth of nanowires in the other two directions, resulting in PNAs with a consistent orientation. Moreover, these PNAs exhibit low-threshold and stable amplified spontaneous emission under one-, two-, and three-photon excitation, indicating their potential for an integrated laser array.

Vertical Conductive Metal-Organic Framework Single-Crystalline Nanowire Arrays for Efficient Electrocatalytic Hydrogen Evolution.

The construction of crystalline metal-organic frameworks with regular architectures supportive of enhanced mass transport and bubble diffusion is imperative for electrocatalytic applications; however, this poses a formidable challenge. Here, a method is presented that confines the growth of nano-architectures to the liquid-liquid interface. Using this method, vertically oriented single crystalline nanowire arrays of an Ag-benzenehexathiol (BHT) conductive metal-organic framework (MOF) are fabricated via an "in-plane self-limiting and out-of-plane epitaxial growth" mechanism. This material has excellent electrocatalytic features, including highly exposed active sites, intrinsically high electrical conductivity, and superhydrophilic and superaerophobic properties. Leveraging these advantages, the carefully designed material demonstrates superior electrocatalytic hydrogen evolution activity, resulting in a low Tafel slope of 66 mV dec-1 and a low overpotential of 275 mV at a high current density of 1 A cm-2. Finite element analysis (FEA) and in situ microscopic verification indicates that the nanowire array structure significantly enhances the electrolyte transport kinetics and promotes the rapid release of gas bubbles. The findings highlight the potential of using MOF-based ordered nanoarray structures for advanced electrocatalytic applications.

Optimized absorption of light in perovskite nanowire solar cells.

Metal halide perovskite nanowires (PrvNWs) have recently emerged as an interesting path for nanostructured solar cells. Here, we model the absorption of light in PrvNW arrays for varying diameter and length of the PrvNWs and period for the array by solving the Maxwell equations. For long enough bare PrvNW arrays, we find that the optimum diameter is fixed to that which places the absorption peak from the HE11waveguide mode in the PrvNWs to the vicinity of the bandgap wavelength. In contrast, when we include a transparent conductive oxide (TCO) top contact layer, the optimum diameter shifts to a larger value by 100 nm. The origin of this shift is traced to a reduced reflection at the interface between the TCO layer and the PrvNW array when the PrvNW's diameter is larger. Overall, we find that 1500 nm long PrvNWs can reach 90% of the broadband absorption potential, making this system of high interest for photovoltaics.

Enhanced LWIR response of InP/InAsP quantum discs-in-nanowire array photodetectors by photogating and ultra-thin ITO contacts.

Here we report on an experimental and theoretical investigation of the long-wavelength infrared (LWIR) photoresponse of photodetectors based on arrays of three million InP nanowires with axially embedded InAsP quantum discs. An ultra-thin top indium tin oxide contact combined with a novel photogating mechanism facilitates an improved LWIR normal incidence sensitivity in contrast to traditional planar quantum well photodetectors. The electronic structure of the quantum discs, including strain and defect-induced photogating effects, and optical transition matrix elements were calculated by an 8-bandk·psimulation along with solving drift-diffusion equations to unravel the physics behind the generation of narrow linewidth intersubband signals observed from the quantum discs.

Conformal Coverage of ZnO Nanowire Arrays by ZnMnO3 : Room-temperature Photodeposition from Aqueous Solution.

Compositionally and structurally complex semiconductor oxide nanostructures gain importance in many energy-related applications. Simple and robust synthesis routes ideally complying with the principles of modern green chemistry are therefore urgently needed. Here we report on the one-step, room-temperature synthesis of a crystalline-amorphous biphasic ternary metal oxide at the ZnO surface using aqueous precursor solutions. More specifically, conformal and porous ZnMnO3 shells are photodeposited from KMnO4 solution onto immobilized ZnO nanowires acting not only as the substrate but also as the Zn precursor. This water-based, low temperature process yields ZnMnO3 /ZnO composite electrodes featuring in 1 M Na2 SO4 aqueous solution capacitance values of 80-160 F g-1 (as referred to the total mass of the porous film i. e. the electroactive ZnMnO3 phase and the ZnO nanowire array). Our results highlight the suitability of photodeposition as a simple and green route towards complex functional materials.

Towards high photoresponse of perovskite nanowire/copper phthalocyanine heterostructured photodetector.

One-dimensional nanowire structures composed of perovskite are widely recognized for their exceptional optoelectronic performance and mechanical properties, making them a popular area of investigation in photodetection research. In this work, a perovskite nanowire/copper phthalocyanine heterojunction-based photodetector was fabricated, which exhibits high photoresponse in the visible-near-infrared region. The incorporation of a heterojunction significantly enhanced the photoelectric performance. Specifically, the photoresponsivity and external quantum efficiency of the nanowire-based device were elevated from 58.5 A W-1and 1.35 × 104% to 84.5 A W-1and 1.97 × 104% at 532 nm, respectively. The enhanced photoresponse of the heterojunction device can be attributed to the unique microstructure of nanowire arrays. The wrapping of the nanowires by copper phthalocyanine forms heterojunctions with a larger dissociation area, which facilitated exciton dissociation and enhanced device performance. This work provides a promising example for optimizing the performance of nanowire devices.

Beyond ray optics absorption of light in CsPbBr3perovskite nanowire arrays studied experimentally and with wave optics modelling.

We study experimentally and with wave optics modelling the absorption of light in CsPbBr3perovskite nanowire arrays fabricated into periodic pores of an anodized aluminum oxide matrix, for nanowire diameters from 30 to 360 nm. First, we find that all the light that couples into the array can be absorbed by the nanowires at sufficient nanowire length. This behavior is in strong contrast to the expectation from a ray-optics description of light where, for normally incident light, only the rays that hit the cross-section of the nanowires can be absorbed. In that case, the absorption in the sample would be limited to the area fill factor of nanowires in the hexagonal array, which ranges from 13% to 58% for the samples that we study. Second, we find that the absorption saturates already at a nanowire length of 1000-2000 nm, making these perovskite nanowires promising for absorption-based applications such as solar cells and photodetectors. The absorption shows a strong diameter dependence, but for all diameters the transmission is less than 24% already at a nanowire length of 500 nm. For some diameters, the absorption exceeds that of a calculated thin film with 100% coverage. Our analysis indicates that the strong absorption in these nanowires originates from light-trapping induced by the out-of-plane disorder due to random axial position of each nanowire within its pore in the matrix.

Photoelectrochemical Nitrate Reduction to Ammonia on Ordered Silicon Nanowire Array Photocathodes.

As a new path to "green" ammonia production, photoelectrochemical nitrate reduction reaction (PEC NO3 RR) is investigated for the first time. An Au-decorated ordered silicon nanowire (O_SiNW) array photocathode demonstrates 95.6 % of Faradaic efficiency (FE) to ammonia at 0.2 VRHE , which represents a more positive potential than the thermodynamic reduction potential of nitrate by utilizing photovoltage. The high FE is possible because both Si and Au surfaces are inactive for competing water reduction to hydrogen. The O_SiNW array structure is favorable to promote the PEC NO3 RR relative to planar Si or randomly-grown Si nanowire, by enabling the uniform distribution of small Au nanoparticles as an electrocatalyst and facilitating the mass transport during the reaction. The results demonstrate the feasibility of PEC nitrate conversion to ammonia and would motivate further studies and developments.

Light Absorption in Nanowire Photonic Crystal Slabs and the Physics of Exceptional Points: The Shape Shifter Modes.

Semiconductor nanowire arrays have been demonstrated as promising candidates for nanoscale optoelectronics applications due to their high detectivity as well as tunable photoresponse and bandgap over a wide spectral range. In the infrared (IR), where these attributes are more difficult to obtain, nanowires will play a major role in developing practical devices for detection, imaging and energy harvesting. Due to their geometry and periodic nature, vertical nanowire and nanopillar devices naturally lend themselves to waveguide and photonic crystal mode engineering leading to multifunctional materials and devices. In this paper, we computationally develop theoretical basis to enable better understanding of the fundamental electromagnetics, modes and couplings that govern these structures. Tuning the photonic response of a nanowire array is contingent on manipulating electromagnetic power flow through the lossy nanowires, which requires an intimate knowledge of the photonic crystal modes responsible for the power flow. Prior published work on establishing the fundamental physical modes involved has been based either on the modes of individual nanowires or numerically computed modes of 2D photonic crystals. We show that a unified description of the array key electromagnetic modes and their behavior is obtainable by taking into account modal interactions that are governed by the physics of exceptional points. Such models that describe the underlying physics of the photoresponse of nanowire arrays will facilitate the design and optimization of ensembles with requisite performance. Since nanowire arrays represent photonic crystal slabs, the essence of our results is applicable to arbitrary lossy photonic crystals in any frequency range.

Cation Exchange Strategy to Single-Atom Noble-Metal Doped CuO Nanowire Arrays with Ultralow Overpotential for H2O Splitting.

Single-atom site catalysts (SACs) have aroused enormous attention and brought about new opportunities for many applications. Herein, we report a versatile strategy to rhodium (Rh) SAC by a facile cation exchange reaction. Remarkably, the Rh SAC modified CuO nanowire arrays on copper foam (Rh SAC-CuO NAs/CF) show unprecedented alkaline oxygen evolution reaction (OER) activity with a high current density of 84.5 mA cm-2@1.5 V vs reversible hydrogen electrode (RHE), 9.7 times that of Ir/C/CF. More strikingly, when used as an anode and a cathode for overall water splitting, the Rh SAC-CuO NAs/CF can achieve 10 mA cm-2 at only 1.51 V. Density functional theory calculations reveal that the high OER and HER intrinsic catalytic activities result from moderate adsorption energy of intermediates on Rh SAC. Finally, we demonstrate the general synthesis of different single-atom noble-metal catalysts on CuO NAs (M SAC-CuO NAs/CF, where M = Ru, Ir, Os, and Au).

Self-powered cathodic photoelectrochemical aptasensor based on in situ-synthesized CuO-Cu2O nanowire array for detecting prostate-specific antigen.

A facile and sensitive self-powered cathodic photoelectrochemical (PEC) aptasensor is reported for the detection of prostate-specific antigen (PSA) based on CuO-Cu2O nanowire array grown on Cu mesh (CuO-Cu2O NWA/CM) as electrode. The mixed narrow band gaps of the CuO-Cu2O heterostructure ensured its wide absorption band, effective electron/hole separation, and high photocatalytic activity in the visible region. In addition, nanowires directly grown on the substrate provided high specific surface area and exposed abundant active sites, thus guaranteeing its high photocatalytic efficiency. Therefore, the self-powered sensor exhibited favorable analytical performance with fast response, wide linear ranges of 0.01 to 5 ng/mL and 5 to 100 ng/mL, an acceptable detection limit of 3 pg/mL, and reasonable selectivity and stability. The proposed CuO-Cu2O NWA/CM can be considered a promising visible light-responsive photoactive material for fabrication of PEC aptasensor with high performance. Graphical abstract a Schematic illustration of construction process of PEC sensing platform based on the CuO-Cu2O composite for PSA detection. b Schematic mechanism of the operating PEC system.

High Responsivity of InP/InAsP Nanowire Array Broadband Photodetectors Enhanced by Optical Gating.

High-performance photodetectors operating in the near-infrared (0.75-1.4 µm) and short-wave infrared (1.4-3.0 µm) portion of the electromagnetic spectrum are key components in many optical systems. Here, we report on a combined experimental and theoretical study of square millimeter array infrared photodetectors comprising 3 million n+-i-n+ InP nanowires grown by MOVPE from periodically ordered Au seed particles. The nominal i-segment, comprising 20 InAs0.40P0.60 quantum discs, was grown by use of an optimized Zn doping to compensate the nonintentional n-doping. The photodetectors exhibit bias- and power-dependent responsivities reaching record-high values of 250 A/W at 980 nm/20 nW and 990 A/W at 532 nm/60 nW, both at 3.5 V bias. Moreover, due to the embedded quantum discs, the photoresponse covers a broad spectral range from about 0.70 to 2.5 eV, in effect outperforming conventional single InGaAs detectors and dual Si/Ge detectors. The high responsivity, and related gain, results from a novel proposed photogating mechanism, induced by the complex charge carrier dynamics involving optical excitation and recombination in the quantum discs and interface traps, which reduces the electron transport barrier between the highly doped n+ contact and the i-segment. The experimental results obtained are in perfect agreement with the proposed theoretical model and represent a significant step forward toward understanding gain in nanoscale photodetectors and realization of commercially viable broadband photon detectors with ultrahigh gain.

Ultraflexible Nanowire Array for Label- and Distortion-Free Cellular Force Tracking.

Living cells interact with their immediate environment by exerting mechanical forces, which regulate important cell functions. Elucidation of such force patterns yields deep insights into the physics of life. Here we present a top-down nanostructured, ultraflexible nanowire array biosensor capable of probing cell-induced forces. Its universal building block, an inverted conical semiconductor nanowire, greatly enhances both the functionality and the sensitivity of the device. In contrast to existing cellular force sensing architectures, microscopy is performed on the nanowire heads while cells deflecting the nanowires are confined within the array. This separation between the optical path and the cells under investigation excludes optical distortions caused by cell-induced refraction, which can give rise to feigned displacements on the 100 nm scale. The undistorted nanowire displacements are converted into cellular forces via the nanowire spring constant. The resulting distortion-free cellular force transducer realizes a high-resolution and label-free biosenor based on optical microscopy. Its performance is demonstrated in a proof-of-principle experiment with living Dictyostelium discoideum cells migrating through the nanowire array. Cell-induced forces are probed with a resolution of 50 piconewton, while the most flexible nanowires promise to enter the 100 femtonewton realm.

Evanescent Wave-Guided Growth of an Organic Supramolecular Nanowire Array.

The ordered assembly of molecules within a specific space of nanoscale, such as a surface, holds great promise in advanced micro-/nanostructure fabrication for various applications. Herein, we demonstrate the evanescent wave (EW)-guided organization of small molecules into a long-range ordered nanowire (NW) array. Experiment and simulation revealed that the orientation and periodicity of the NW array were feasibly regulated by altering the propagation direction and the wavelength of EW. The generality of this approach was demonstrated by using different molecule precursors. While existing studies on EW often took advantages of its near-field property for optical sensing, this work demonstrated the photochemical power of EW in the guided-assembly of small molecules for the first time. It also provides an enlightening avenue to periodic structure with fluorescence, promising for super-resolution microscopy and important devices applicable to optical and bio-related fields.

Ultracompliant Heterogeneous Copper-Tin Nanowire Arrays Making a Supersolder.

Due to the substantial increase in power density, thermal interface resistance that can constitute more than 50% of the total thermal resistance has generally become a bottleneck for thermal management in electronics. However, conventional thermal interface materials (TIMs) such as solder, epoxy, gel, and grease cannot fulfill the requirements of electronics for high-power and long-term operation. Here, we demonstrate a high-performance TIM consisting of a heterogeneous copper-tin nanowire array, which we term "supersolder" to emulate the role of conventional solders in bonding various surfaces. The supersolder is ultracompliant with a shear modulus 2-3 orders of magnitude lower than traditional solders and can reduce the thermal resistance by two times as compared with the state-of-the-art TIMs. This supersolder also exhibits excellent long-term reliability with >1200 thermal cycles over a wide temperature range. By resolving this critical thermal bottleneck, the supersolder enables electronic systems, ranging from microelectronics and portable electronics to massive data centers, to operate at lower temperatures with higher power density and reliability.

A Robust Highly Aligned DNA Nanowire Array-Enabled Lithography for Graphene Nanoribbon Transistors.

Because of its excellent charge carrier mobility at the Dirac point, graphene possesses exceptional properties for high-performance devices. Of particular interest is the potential use of graphene nanoribbons or graphene nanomesh for field-effect transistors. Herein, highly aligned DNA nanowire arrays were crafted by flow-assisted self-assembly of a drop of DNA aqueous solution on a flat polymer substrate. Subsequently, they were exploited as "ink" and transfer-printed on chemical vapor deposited (CVD)-grown graphene substrate. The oriented DNA nanowires served as the lithographic resist for selective removal of graphene, forming highly aligned graphene nanoribbons. Intriguingly, these graphene nanoribbons can be readily produced over a large area (i.e., millimeter scale) with a high degree of feature-size controllability and a low level of defects, rendering the fabrication of flexible two terminal devices and field-effect transistors.

Effects of Nanowire Length and Surface Roughness on the Electrochemical Sensor Properties of Nafion-Free, Vertically Aligned Pt Nanowire Array Electrodes.

In this paper, vertically aligned Pt nanowire arrays (PtNWA) with different lengths and surface roughnesses were fabricated and their electrochemical performance toward hydrogen peroxide (H2O2) detection was studied. The nanowire arrays were synthesized by electroplating Pt in nanopores of anodic aluminum oxide (AAO) template. Different parameters, such as current density and deposition time, were precisely controlled to synthesize nanowires with different surface roughnesses and various lengths from 3 µm to 12 µm. The PtNWA electrodes showed better performance than the conventional electrodes modified by Pt nanowires randomly dispersed on the electrode surface. The results indicate that both the length and surface roughness can affect the sensing performance of vertically aligned Pt nanowire array electrodes. Generally, longer nanowires with rougher surfaces showed better electrochemical sensing performance. The 12 µm rough surface PtNWA presented the largest sensitivity (654 µA·mM⁻¹·cm⁻²) among all the nanowires studied, and showed a limit of detection of 2.4 µM. The 12 µm rough surface PtNWA electrode also showed good anti-interference property from chemicals that are typically present in the biological samples such as ascorbic, uric acid, citric acid, and glucose. The sensing performance in real samples (river water) was tested and good recovery was observed. These Nafion-free, vertically aligned Pt nanowires with surface roughness control show great promise as versatile electrochemical sensors and biosensors.

Crystal phase-dependent nanophotonic resonances in InAs nanowire arrays.

Nanostructures have many material, electronic, and optical properties that are not found in bulk systems and that are relevant for technological applications. For example, nanowires realized from III-V semiconductors can be grown into a wurtzite crystal structure. This crystal structure does not naturally exist in bulk where these materials form the zinc-blende counterpart. Being able to concomitantly grow these nanowires in the zinc-blende and/or wurtzite crystal structure provides an important degree of control for the design and optimization of optoelectronic applications based on these semiconductor nanostructures. However, the refractive indices of this new crystallographic phase have so far not been elucidated. This shortcoming makes it impossible to predict and utilize the full potential of these new nanostructured materials for optoelectronics applications: a careful design and optimization of optical resonances by tuning the nanostructure geometry is needed to achieve optimal performance. Here, we report and analyze striking differences in the optical response of nanophotonic resonances in wurtzite and zinc-blende InAs nanowire arrays. Specifically, through reflectance measurements we find that the resonance can be tuned down to λ ≈ 380 nm in wurtzite nanowires by decreasing the nanowire diameter. In stark contrast, a similar tuning to below λ ≈ 500 nm is not possible in the zinc-blende nanowires. Furthermore, we find that the wurtzite nanowires can absorb twice as strongly as the zinc-blende nanowires. We attribute these strikingly large differences in resonant behavior to large differences between the refractive indices of the two crystallographic phases realized in these nanostructures. We anticipate our findings to be relevant for other III-V materials as well as for all material systems that manifest polytypism. Taken together, our results demonstrate crystal phase engineering as a potentially new design dimension for optoelectronics applications.

Deviatoric stress-driven fusion of nanoparticle superlattices.

We model the mechanical response of alkanethiol-passivated gold nanoparticle superlattice (supercrystal) at ambient and elevated pressures using large-scale molecular dynamics simulation. Because of the important roles of soft organic ligands in mechanical response, the supercrystals exhibit entropic viscoelasticity during compression at ambient pressure. Applying a hydrostatic pressure of several hundred megapascals on the superlattice, combined with a critical deviatoric stress of the same order along the [110] direction of the face-centered-cubic supercrystal, can drive the room-temperature sintering ("fusion") of gold nanoparticles into ordered gold nanowire arrays. We discuss the molecular-level mechanism of such phenomena and map out a nonequilibrium stress-driven processing diagram, which reveals a region in stress space where fusion of nanoparticles can occur, instead of other competing plasticity or phase transformation processes in the supercrystal. We further demonstrate that, for silver-gold (Ag-Au) binary nanoparticle superlattices in sodium chloride-type superstructure, stress-driven fusion along the [100] direction leads to the ordered formation of Ag-Au multijunction nanowire arrays.

Activation of multiple signaling pathways during the differentiation of mesenchymal stem cells cultured in a silicon nanowire microenvironment.

Mesenchymal stem cells (MSC) offer an optimal source for bone tissue engineering due to their capability of undergoing multilineage differentiation, where the mechanical properties of the microenvironment of MSCs are vital for osteochondral formation. However, the mechanisms of how mechanical and microenvironmental cues control osteogenesis and chondrogenesis are yet to be elucidated. In this study, we investigated the effects of vertically aligned silicon nanowire (SiNW) array on the differentiation of MSCs and the associated molecular mechanisms involved in osteogenesis and chandrogenesis. The results showed that the microenvironment of SiNW array activated a number of mechanosensitive pathways (including Integrin, TGF-ß/BMP, Akt, MAPK, Insulin, and Wnt pathways) in MSCs, which converged to stimulate the osteogenesis and chondrogenesis via the Ras-Raf-MEK-ERK cascade. FROM THE CLINICAL EDITOR: This study reports on the mechanisms and microenvironmental influence of osteogenesis and chondrogenesis by mesenchymal stem cells interacting with vertically aligned silicon nanowire scaffolds.