Nanostructure Arrays Research Articles

Self-Assembled Surfactant-Polyoxovanadate Soft Materials as Tuneable Vanadium Oxide Cathode Precursors for Lithium-Ion Batteries.

The mixing of [V10 O28 ]6- decavanadate anions with a dicationic gemini surfactant (gem) leads to the spontaneous self-assembly of surfactant-templated nanostructured arrays of decavanadate clusters. Calcination of the material under air yields highly crystalline, sponge-like V2 O5 (gem-V2 O5 ). In contrast, calcination of the amorphous tetrabutylammonium decavanadate allows isolation of a more agglomerated V2 O5 consisting of very small crystallites (TBA-V2 O5 ). Electrochemical analysis of the materials' performance as lithium-ion intercalation electrodes highlights the role of morphology in cathode performance. The large crystallites and long-range microstructure of the gem-V2 O5 cathode deliver higher initial capacity and superior capacity retention than TBA-V2 O5 . The smaller crystallite size and higher surface area of TBA-V2 O5 allow faster lithium insertion and superior rate performance to gem-V2 O5 .

Self‐Assembled Surfactant‐Polyoxovanadate Soft Materials as Tuneable Vanadium Oxide Cathode Precursors for Lithium‐Ion Batteries

AbstractThe mixing of [V10O28]6− decavanadate anions with a dicationic gemini surfactant (gem) leads to the spontaneous self‐assembly of surfactant‐templated nanostructured arrays of decavanadate clusters. Calcination of the material under air yields highly crystalline, sponge‐like V2O5 (gem‐V2O5). In contrast, calcination of the amorphous tetrabutylammonium decavanadate allows isolation of a more agglomerated V2O5 consisting of very small crystallites (TBA‐V2O5). Electrochemical analysis of the materials’ performance as lithium‐ion intercalation electrodes highlights the role of morphology in cathode performance. The large crystallites and long‐range microstructure of the gem‐V2O5 cathode deliver higher initial capacity and superior capacity retention than TBA‐V2O5. The smaller crystallite size and higher surface area of TBA‐V2O5 allow faster lithium insertion and superior rate performance to gem‐V2O5.

Poly‐N‐isopropylacrylamide Colloidal Arrays as Templates for Droplet‐Assisted Fabrication of Plasmonic Nanostructure Patterns

AbstractThe homogeneous and ordered coverage of substrate surfaces with nanostructures is still a challenge and is often tackled today, for example, by inkjet printing. In this case, drying effects in printed liquid droplets can lead to undesired pattern formation. Herein, colloidal arrays of poly‐N‐isopropylacrylamide are used for site‐selective self‐assembly of gold nanoparticles on large areas. The soft colloids support the drying process of gold nanoparticle dispersion droplets and leave room for capillary convection and Marangoni convection flow. This results in homogenous gold nanoparticle arrays with different shapes after drying, which can be converted into solid gold nanostructures by thermal treatment, paving the way for a simple bottom‐up fabrication strategy for highly ordered nanostructure arrays on large areas.

Metallic Plasmonic Nanostructure Arrays for Enhanced Solar Photocatalysis

AbstractPlasmon‐enhanced photocatalysis has emerged as a promising technology for solar‐to‐chemical energy conversion. Compared to isolated or disordered metal nanostructures, by controlling the morphology, composition, size, spacing, and dispersion of individual nanocomponents, plasmonic nanostructure arrays with coupling architectures yield strong broadband light‐harvesting capability, efficient charge transfer, enhanced local electromagnetic fields, and large contact interfaces. Although metallic nanostructure arrays are extensively studied for various applications, such as refractive index sensing, surface‐enhanced spectroscopy, plasmon‐enhanced luminescence, plasmon nanolasing, and perfect light absorption, the connection between surface plasmon resonance and enhanced photocatalysis remains relatively unexplored. In this study, an overview of plasmonic nanostructure arrays over a broad range, from 0D to 3D, for efficient photocatalysis is presented. By reviewing the fundamental mechanisms, recent applications, and latest developments of plasmonic nanostructure arrays in solar‐driven chemical conversion, this study reports on the latest guidance toward the integration of plasmonic nanostructures for functional devices in the fields of plasmonic, photonics, photodetection, and solar‐energy harvesting.

Morphology-Dependent Near-Infrared Electrochromic Properties of Tungsten Oxide

Vertically aligned WO3 nano-architectures on the transparent conducting substrate are produced via a hydrothermal method. The results revealed that different WO3 nano-architectures, including “nanoblocks”, “nanosheet” and “nanobelt” structures, can be obtained by adjusting the composition of the precursor solution, that shows that solvent composition plays an important role in the adjustment of the prepared material morphology. The nanostructured array films with thicknesses of about 600 nm show remarkable enhancement of the electrochromic properties in the infrared region. The obtained WO3 films have good electrochromic properties in the near-infrared range. In particular, significant optical modulation of the WO3 nanosheets (72% at 1200 nm), fast switching speed (6.5 s for colored and 8.7 s for bleached), and excellent cycling stability (maintained 90.2% of the initial optical modulation after 1000 cycles). The improved electrochromic performance is mainly due to the vertically arranged structure, which makes it easier for ions to diffuse in the nanoarray, and also provides a larger surface area for charge transfer reaction. The research results provide a certain reference value for the research of electrochromic near-infrared performance.

Self-assembly of Au nanocrystals into large-area 3-D ordered flexible superlattice nanostructures arrays for ultrasensitive trace multi-hazard detection.

Plasmonic nanoparticles that self-assemble into highly ordered superlattice nanostructures hold substantial promise for facilitating ultra-trace surface-enhanced Raman scattering (SERS) detection. Herein, we propose a boiling-point evaporation method to synthesize ordered monocrystal-like superlattice Au nanostructures (OML-Au NTs) with a polyhedral morphology. Combined with thermal nanoimprint technology, OML-Au NTs were directly transferred to impact-resistant polystyrene (IPS) flexible SERS substrates, the obtained flexible substrates (donated as OML-Au NTs/IPS) detection limit for R6G molecules as low as 10-13 M. These results were confirmed by simulating the electromagnetic field distribution of ordered/unordered two-dimensional single-layer and three-dimensional aggregated gold nanostructures. The OML-Au NTs/IPS substrates were successfully used to detect and quantify three commonly-used agricultural pesticides, achieving detection limits as low as 10-11 M and 10-12 M, and in situ real-time detection limit reached 0.24pg/cm2 for thiram on apple peels, which was 3 orders of magnitude lower than the current detection limit. In addition, the Raman intensity from multiple locations showed a relative standard deviation lower than 7 %, exhibiting the reliability necessary for practical applications. As a result, this research demonstrates a highly reproducible method to enable the development of plasmonic nanomaterials with flexible superstructures.

Construction of 3D Hierarchical Co3O4@CoFe-LDH Heterostructures with Effective Interfacial Charge Redistribution for Rechargeable Liquid/Solid Zn-Air Batteries.

Constructing three-dimensional (3D) hierarchical heterostructures is an appealing but challenging strategy to improve the performance of catalysts for electrical energy devices. Here, an efficient and robust flexible self-supporting catalyst, interface coupling of ultrathin CoFe-LDH nanosheets and Co3O4 nanowire arrays on the carbon cloth (CC/Co3O4@CoFe-LDH), was proposed for boosting oxygen evolution reaction (OER) in rechargeable liquid/solid Zn-air batteries (ZABs). The strong interfacial interaction between the CoFe-LDH and Co3O4 heterostructures stimulated the charge redistribution in their coupling regions, which improved the electron conductivity and optimized the adsorption free energy of OER intermediates, ultimately boosting the intrinsic OER performance. Besides, the 3D hierarchical nanoarray structure facilitated the exposure of catalytically active centers and rapid electron/mass transfer during the OER process. As such, the CC/Co3O4@CoFe-LDH catalyst achieved excellent OER catalytic activity in alkaline medium, with a small overpotential of 237 mV at 10 mA cm-2, a low Tafel slope of 35.43 mV dec-1, and long-term durability of up to 48 h, significantly outperforming the commercial RuO2 catalyst. More impressively, the liquid and flexible solid-state ZABs assembled by the CC/Co3O4@CoFe-LDH hybrid catalyst as the OER catalyst presented a stable open circuit voltage, large power density, superb cycling life, and satisfactory flexibility, indicating great potential applications in energy technology. This work provides a good guidance for the development of advanced electrocatalysts with heterostructures and an in-depth understanding of electronic modulation at the heterogeneous interface.

Fluorescence Intensity of Liposomes and E. coli Attached to Nanopillar Arrays: Implications for Bacterial Death on Nanostructures

Bacterial death on nanostructures has sparked great interest because the principle behind this phenomenon completely differs from that of conventional chemical antimicrobial agents. Physical interactions between the bacterial envelope and nanostructures generate forces that deform the cell membrane. Eventually, the cell envelope breaks, causing the cytoplasm to leak out. However, the events occurring between these stages are unclear. In this work, we used liposomes as pseudocells because they are composed of a lipid bilayer, which is similar to a cytoplasmic membrane. We monitored time-dependent changes in the fluorescence intensities of rhodamine 6G (R6G)-containing liposomes and mCherry-expressing Escherichia coli cells after adhering to Au nanostructure arrays (pitch; height; diameter = 500, 300, 283 nm) and compared the variations in the fluorescence intensities of the pseudo and E. coli cells over time. Electrochemical impedance spectroscopy was then performed to monitor the cell and liposome attachment. Ratio of change in Rct before and after the liposome injection was about 1.7, which means that Rct increased drastically due to the attachment of liposome. Similarly, ratio of change in Rct before and after the E. coli injection was about 1.15 due to the attachment of cell. The fluorescence intensity of mCherry quickly decreased after cell adhesion within 25 min, whereas that of R6G did not even at 60 min. This finding means that the liposomes were not broken down despite their mechanical strength being equal to or weaker than that of E. coli. The time constant (T) of the decrease in fluorescence intensity of E. coli was calculated by fitting the data to an exponential function and found to be −0.13 min–1, which is in good agreement with our previous results. But we could not calculate the T of liposomes. The results indicate that the death of bacteria on nanostructures likely involves an autolytic mechanism.

In situ transformation of hierarchical FeOOH/CuO arrays with electro-cleaning capability for oil-in-water emulsion separation and electro-fenton degradation of organic dye

With the increasing oily wastewater discharges and crude oil leakage accidents, the eco-environment and human health is seriously harmed. Membrane technology is an ideal choice for industrial oil/water separation, but the gradually structural fouling has severely hampered the long-term practical applications. Herein, membrane separation, electroflotation and electro-Fenton technologies are successfully coupled through structural design and regulation. The FeOOH nanosheet/CuO nanowire coated on copper mesh is prepared via chemical oxidation and thermal dehydration. The FeOOH nanosheets are in situ converted and tightly encapsulated on the surface of CuO nanowires, while the hierarchical nano-array structure and interconnected FeOOH coating ensure the superhydrophilic, underwater superoleophobic and electroflotation self-cleaning capabilities. Therefore, the 3*Fe/CuO-5 membrane exhibits high water flux (≥1400 L h−1 m−2), separation efficiency (≥99.2%) and excellent electroflotation self-cleaning capability (within 2 min) in oil-in-water emulsion separation. Moreover, the heterogeneous electro-Fenton system composed of 3*Fe/CuO-5 membrane exhibits good degradation efficiency of 30 mg L−1 methylene blue within 100 min. Thus, the as-prepared 3*Fe/CuO-5 membrane is promising in industrial wastewater purification due to its rapid oil separation and soluble organic purification ability.

Plasmon-Exciton Coupling Effect in Nanostructured Arrays for Optical Signal Amplification and SARS-CoV-2 DNA Sensing.

A surface plasmon resonance (SPR)-enhanced optical signal using a nanoslit array and acridine orange (AO) dye system at a flexible poly(dimethylsiloxane) (PDMS) substrate was achieved in this work and demonstrated a simple sensing scheme to directly detect SARS-CoV-2 nucleic acid via DNA hybridization. A simple nanoimprinting pattern transfer technique was introduced to form uniform reproducible nanoslit arrays where the dimensions of the slit array were controlled by the thickness of the gold film. The plasmon-exciton coupling effect on the optical enhancement of different dye molecules, i.e., AO, propidium iodide (PI), or dihydroethidium (DHE) attached to the nanoslit surfaces, was examined thoroughly by measuring the surface reflection and fluorescence imaging. The results indicate that the best overlap of the plasmon resonance wavelength to the excitation spectrum of AO presented the largest optical enhancement (∼57×) compared to the signal at flat gold surfaces. Based on this finding, a sensitive assay for detecting DNA hybridization was generated using the interaction of the selected SARS-CoV-2 ssDNA and dsDNA with AO to trigger the metachromatic behavior of the dye at the nanoarray surfaces. We found strong optical signal amplification on the formation of acridine-ssDNA complexes and a quenched signal upon hybridization to the complementary target DNA (ct-DNA) along with a blue shift in the fluorescence of AO-dsDNAs. A quantitative evaluation of the ct-DNA concentration in a range of 100-0.08 nM using both the reflection and emission imaging signals demonstrated two linear regimes with a lowest detection limit of 0.21 nM. The sensing method showed high sensitivity and distinguished signals from 1-, 2-, and 3-base mismatched DNA targets, as well as high stability and reusability. This approach toward enhancing optical signal for DNA sensing offers promise in a general, rapid, and direct vision detection method for nucleic acid analytes.

Computational Investigation of Advanced Refractive Index Sensor Using 3-Dimensional Metamaterial Based Nanoantenna Array.

Photonic researchers are increasingly exploiting nanotechnology due to the development of numerous prevalent nanosized manufacturing technologies, which has enabled novel shape-optimized nanostructures to be manufactured and investigated. Hybrid nanostructures that integrate dielectric resonators with plasmonic nanostructures are also offering new opportunities. In this work, we have explored a hybrid coupled nano-structured antenna with stacked multilayer lithium tantalate (LiTaO3) and Aluminum oxide (Al2O3), operating at wavelength ranging from 400 nm to 2000 nm. Here, the sensitivity response has been explored of these nano-structured hybrid arrays. It shows a strong electromagnetic confinement in the separation gap (g) of the dimers due to strong surface plasmon resonance (SPR). The influences of the structural dimensions have been investigated to optimize the sensitivity. The designed hybrid coupled nanostructure with the combination of 10 layers of gold (Au) and Lithium tantalate (LiTaO3) or Aluminum oxide (Al2O3) (five layers each) having height, h1 = h2 = 10 nm exhibits 730 and 660 nm/RIU sensitivity, respectively. The sensitivity of the proposed hybrid nanostructure has been compared with a single metallic (only gold) elliptical paired nanostructure. Depending on these findings, we demonstrated that a roughly two-fold increase in the sensitivity (S) can be obtained by utilizing a hybrid coupled nanostructure compared to an identical nanostructure, which competes with traditional sensors of the same height, (h). Our innovative novel plasmonic hybrid nanostructures provide a framework for developing plasmonic nanostructures for use in various sensing applications.

A Review on Fabrication and Application of Tunable Hybrid Micro–Nano Array Surfaces

AbstractThe wettability and adhesion of biological surfaces often depend on their periodically arranged hybrid micro–nano array structures. Various fabrication processes are designed to mimic biomimetic micro–nano array surfaces. This review summarizes the types of micro–nano array structures and analyzes fabrication methods based on top‐down and bottom‐up construction, including templating, etching, self‐assembly, and electrospinning/electrospraying. This review focuses on the shape reconfiguration of surface micro–nano array structures under physical stimuli, as well as the changes in material surface properties during the reconfiguration process. In addition, the applications of biomimetic micro–nano array composite surfaces in the fields of droplet transport, adhesion properties, sensors, and soft robotics are also discussed, and the current challenges and prospects in this field are identified.

Discotic Liquid Crystals with Highly Ordered Columnar Hexagonal Structure for Ultraviolet Light-Sensitive Phototransistor Memory

Organic phototransistors have been vigorously investigated for their superior charge-transport performance, photosensitivity, and compatibility with integrated circuits. Accordingly, liquid crystal molecules have been proven to be a high-performance organic electret, and discotic liquid crystal with a face-on orientation is able to show ultrafast photoresponse. Thus far, there is still no application of discotic liquid crystal as a charge-trapping electret in phototransistors. In this study, a series of discotic liquid crystalline molecules consisting of alkyl-triphenylene (Cx-TP, where x = 1, 6, 8, and 10) were designed and applied as an electret in the ultraviolet light-sensitive photomemory. The discotic liquid crystal with optimized side-chain length produced a homeotropically aligned nanoarray structure and endowed the best performance and photoresponse in phototransistor memory. Therefore, C6-TP- and C8-TP-based devices produced high memory ratios of approximately 103 and 104, respectively, which outperformed their analogues of C1-TP and C10-TP with a memory ratio of approximately 102. This achievement indicates the columnar hexagonal structure induced by the homeotropic alignment during liquid crystalline transition produces a huge impact on the photoresponse and device performance. The result of this study underlines the potential of discotic liquid crystals as a photoactive electret in phototransistor applications.

Novel in-situ deposited V2O5 nanorods array film sensor with enhanced gas sensing performance to n-butylamine

The regular and ordered arrangement of nanoarrays structure can provide effective transmission channels for the adsorption and desorption of gas molecules, and its excellent stability makes it have great advantages as a gas sensing material, which also poses challenges for the preparation of materials. In this work, V2O5 nanorods array was grown in-situ on ceramic tubes without seed layers by means of one-step solvothermal method. The structural characterization showed that the V2O5 nanorods array structure completely covered the surface of the ceramic tube. The gas sensing test results showed that the V2O5 nanorods array sensor had high response (100 ppm, Ra/Rg = 10.8), low detection limit (100 ppb), good reproducibility and long-term stability to n-butylamine. Its excellent sensing performance can be conributed to the fact that the array structure of nanorods can provide more active surfaces, and a great deal of gaps are formed between stacked nanorods, which is helpful to rapid response and recovery of gases. Moreover, from the perspective of the array structure of V2O5 nanorods and the chemical oxidation–reduction process, the possible detection mechanism of n-butylamine by the sensor was also discussed. The excellent gas sensing performance has the latent application prospect in the detection of trace amine gases.

Highly Heterogeneous Morphology of Cobalt Oxide Nanostructures for the Development of Sensitive and Selective Ascorbic Acid Non-Enzymatic Sensor

The surface tailored metal oxide nanostructures for the development of non-enzymatic sensors are highly demanded, but it is a big task due to the wide range of complexities during the growth process. The presented study focused on the surface modification of the heterogeneous morphology of cobalt oxide (Co3O4) prepared by the hydrothermal method. Further surface modification was conducted with the use of sodium citrate as a reducing and surface modifying agent for the Co3O4 nanostructures through the high density of oxygenated terminal groups from the citrate ions. The citrate ions enabled a significant surface modification of the Co3O4 nanostructures, which further improved the electrochemical properties of the Co3O4 material toward the design of the non-enzymatic ascorbic acid sensor in a phosphate buffer solution of pH 7.4. The morphology and crystal arrays of the Co3O4 nanostructures were studied by scanning electron microscopy (SEM) and powder X-ray diffraction (XRD) techniques. These physical characterizations showed the highly tailored surface features of Co3O4 nanostructures and a significant impact on the crystal properties. The electrochemical activity of Co3O4 was studied by chronoamperometry, linear sweep voltammetry, and cyclic voltammetry (CV) for the detection of ascorbic acid. The linear range of the proposed sensor was measured from 0.5 mM to 6.5 mM and a low limit of detection of 0.001 mM was also estimated. The presented Co3O4 nanostructures exhibited significant surface roughness and surface area, consequently playing a vital role toward the selective, sensitive, and stable detection of ascorbic acid. The use of a low cost surface modifying agent such as sodium citrate could be of great interest for the surface roughness and high surface area of nanostructured materials for the improved electrochemical properties for the biomedical, energy storage, and conversion systems.

Three-dimensionally reconfigurable focusing of laser by mechanically tunable metalens doublet with built-in holograms for alignment

Abstract Metalenses have potential to replace various bulky conventional optical elements with ultrathin nanostructure arrays. In particular, active metalenses with reconfigurable focusing capability have attracted considerable interest from the academic and industrial communities. However, their tuning range is currently restricted by limited material properties and fabrication difficulties. Here, a hybrid optical system capable of three-dimensional relocation of a focal spot is proposed and experimentally demonstrated. The system comprises a mechanically actuated passive metalens doublet that can be easily fabricated with commonly available materials and processes. An incident laser can be focused to a desired point in three-dimensional space simply by rotating two metalenses or changing their separation. In addition, exploiting the polarization-multiplexing capability of metasurfaces, a hologram is incorporated to the metalenses to guide rotational and positional alignment of two metasurfaces. The ease of fabrication and alignment provided by this approach could widen its application to many practical fields.

Autonomous discovery of emergent morphologies in directed self-assembly of block copolymer blends.

The directed self-assembly (DSA) of block copolymers (BCPs) is a powerful approach to fabricate complex nanostructure arrays, but finding morphologies that emerge with changes in polymer architecture, composition, or assembly constraints remains daunting because of the increased dimensionality of the DSA design space. Here, we demonstrate machine-guided discovery of emergent morphologies from a cylinder/lamellae BCP blend directed by a chemical grating template, conducted without direct human intervention on a synchrotron x-ray scattering beamline. This approach maps the morphology-template phase space in a fraction of the time required by manual characterization and highlights regions deserving more detailed investigation. These studies reveal localized, template-directed partitioning of coexisting lamella- and cylinder-like subdomains at the template period length scale, manifesting as previously unknown morphologies such as aligned alternating subdomains, bilayers, or a "ladder" morphology. This work underscores the pivotal role that autonomous characterization can play in advancing the paradigm of DSA.

Self-Assembly of Gyroid-Forming Diblock Copolymers under Spherical Confinement

The self-assembly of gyroid-forming diblock copolymers (diBCPs) confined in spherical cavities was systematically investigated by simulations and experiments. The Monte Carlo simulations were carried out on the single-site bond fluctuation model of two gyroid-forming diBCPs of different volume fractions using the simulated annealing method. The experimental study was performed on gyroid-forming poly(styrene)-b-poly(lactic acid) diBCPs confined in spherical cavities. The cavities were fabricated through the assembly of polystyrene colloids to form opal structures, followed by replacement to form inverse opal structures. The surface of the cavities was composed of hydrophobic polyurethane acrylate and hydrophilic SiO2, providing confining surfaces with a different preference for specific polymeric blocks. It was observed from both the experiments and simulation that, depending on the conditions of spherical confinement, a rich array of nanostructures was self-assembled from the gyroid-forming diBCPs. The morphological predictions of simulations are qualitatively consistent with the experimental observations. The self-assembled structures depend sensitively on the surface selectivity and the degree of confinement quantified by the ratio D/L0, where D and L0 are the spherical diameter and period of the equilibrium gyroid phase, respectively. The formed nanostructured self-supporting spheres have considerable potential for applications in drug release, catalysts, optoelectronic devices, filters, and other applications.

High aspect ratio arrays of Si nano-pillars using displacement Talbot lithography and gas-MacEtch

Structuring Si in arrays of vertical high aspect ratio pillars, ranging from nanoscale to macroscale feature dimensions, is essential for producing functional interfaces for many applications. Arrays of silicon 3D nanostructures are needed to realize photonic and phononic crystals, waveguides, metalenses, X-ray wavefront sensors, detectors. In particular, arrays of Si nanopillars are used as bio-interfaces in neural activity recording, cell culture, microfluidics, sensing and on-chip manipulation. Here, we demonstrate a strategy for realizing arrays of protruding sharp Si nanopillars, using displacement Talbot lithography combined with metal-assisted chemical etching (MacEtch) in gas phase. Such combination enables reliable and low cost pathway for fabrication of ordered nanopillars arrays on large scale. With the double exposure of a linear grating mask in orthogonal orientations and the lift-off technique, we realized a catalyst pattern of holes in a Pt thin film with a period of 1 μm and hole diameter in the range of 100–250 nm. MacEtch in gas phase by using vapor HF and oxygen from air allows to etch arrays of protruding Si nanopillars 200 nm-thick and aspect ratio in the range of 200 (pillar height/width) with an etching rate up to 1 μm/min. Gas-MacEtch has the advantage of no capillary stiction, no ion beam damage of the Si substrate, nanometric resolution and high fidelity of pattern transfer. In combination with controlled uniformity of feature size on large area, spatial frequency doubling and high resolution of Talbot lithography, the proposed method is an easy-to-scale-up processing that can support the fabrication of Si pillars arrays for many valuable applications both at micro and nano-scale.

High-performance antireflection nanostructure arrays on aluminum-doped zinc oxide film fabricated with femtosecond laser near-field processing

Transmittance is critical to the performance of optoelectronic devices, and the fabrication of nanostructure arrays with sizes and periods similar to wavelengths on optical surfaces can effectively reduce reflectance and increase transmittance. A method combining a femtosecond laser and the near-field effect of polystyrene (PS) microspheres to prepare integrated high-performance anti-reflective nanostructure arrays on aluminum-doped zinc oxide (AZO) film was proposed in this study. The near-field effect of microspheres with different diameters on a laser light field for several laser wavelengths was simulated with the finite-difference time-domain (FDTD) method. The simulation results showed that a 10-fold improvement of the intensity of a focused laser beam could be obtained with the combination of an 800-nm laser and 1-μm PS microspheres. Nano-craters on the surface of the AZO film were obtained with femtosecond laser irradiation. The depth and the area of these nano craters both increased with the increase of the laser fluences and tended toward saturation when the fluence went from 0.67 to 0.83 J/cm2. Facilitated by the gradient refractive index formed by the nano-craters, the transmittance of the sample treated with 0.83 J/cm2 increased by 8% in the 400–1100 nm band and even by 15% in the 400–600 nm band. The ablation mechanism was revealed by the time-resolved pump-probe technique, which proved that the nano-craters were formed by the phase explosion, and the smooth bottom with fine cracks was induced by the inhomogeneous resolidification of the superheated liquid phase. Our method could endow a photoelectric device with high-performance integrated anti-reflection capability, eliminating the need for additional anti-reflection coating.