Nanoimprint-induced strain engineering of two-dimensional materials.

The high stretchability of two-dimensional (2D) materials has facilitated the possibility of using external strain to manipulate their properties. Hence, strain engineering has emerged as a promising technique for tailoring the performance of 2D materials by controlling the applied elastic strain field. Although various types of strain engineering methods have been proposed, deterministic and controllable generation of the strain in 2D materials remains a challenging task. Here, we report a nanoimprint-induced strain engineering (NISE) strategy for introducing controllable periodic strain profiles on 2D materials. A three-dimensional (3D) tunable strain is generated in a molybdenum disulfide (MoS2) sheet by pressing and conforming to the topography of an imprint mold. Different strain profiles generated in MoS2 are demonstrated and verified by Raman and photoluminescence (PL) spectroscopy. The strain modulation capability of NISE is investigated by changing the imprint pressure and the patterns of the imprint molds, which enables precise control of the strain magnitudes and distributions in MoS2. Furthermore, a finite element model is developed to simulate the NISE process and reveal the straining behavior of MoS2. This deterministic and effective strain engineering technique can be easily extended to other materials and is also compatible with common semiconductor fabrication processes; therefore, it provides prospects for advances in broad nanoelectronic and optoelectronic devices.

Switchable Power Generation in Triboelectric Nanogenerator Toward Chip-Less Wearable Power Module Applications.

A conceptual shift toward next-generation wearable electronics is driving research into self-powered electronics technologies that can be independently operated without plugging into the grid for external power feeding. Triboelectric nanogenerators (TENGs) are emerging as a key component of self-powered electronics, but a power type mismatch between supply and demand limits their direct implementation into wearable self-powered electronics. Here, a TENG with switchable power mode capability is reported where the charge flow direction is modulated over the course of slow and random mechanical stimuli, with exceptional rectification capabilities as high as ≈133, stable outputs over the cycles, and design flexibility in different platforms. Importantly, the remarkable switchable power generation with fabric counter materials illuminates a new path for the smooth integration of flexible TENGs into wearable self-powered electronics.

Metallic Micro-Nano Network-Based Soft Transparent Electrodes: Materials, Processes, and Applications.

Soft transparent electrodes (TEs) have received tremendous interest from academia and industry due to the rapid development of lightweight, transparent soft electronics. Metallic micro-nano networks (MMNNs) are a class of promising soft TEs that exhibit excellent optical and electrical properties, including low sheet resistance and high optical transmittance, as well as superior mechanical properties such as softness, robustness, and desirable stability. They are genuinely interesting alternatives to conventional conductive metal oxides, which are expensive to fabricate and have limited flexibility on soft surfaces. This review summarizes state-of-the-art research developments in MMNN-based soft TEs in terms of performance specifications, fabrication methods, and application areas. The review describes the implementation of MMNN-based soft TEs in optoelectronics, bioelectronics, tactile sensors, energy storage devices, and other applications. Finally, it presents a perspective on the technical difficulties and potential future possibilities for MMNN-based TE development.

Si/Organic Integrated Narrowband Near-Infrared Photodetector.

Spectrally selective narrowband photodetection is critical for near-infrared (NIR) imaging applications, such as for communicationand night-vision utilities. It is a long-standing challenge for detectors based on silicon, to achieve narrowband photodetection without integrating any optical filters. Here, this work demonstrates a NIR nanograting Si/organic (PBDBT-DTBT:BTP-4F) heterojunction photodetector (PD), which for the first time obtains the full-width-at-half-maximum (FWHM) of only 26 nm and fast response of 74 µs at 895 nm. The response peak can be successfully tailored from 895 to 977 nm. The sharp and narrow response NIR peak is inherently attributed to the coherent overlapping between the NIR transmission spectrum of organic layer and diffraction enhanced absorption peak of patterned nanograting Si substrates. The finite difference time domain (FDTD) physics calculation confirms the resonant enhancement peaks, which is well consistent with the experiment results. Meanwhile, the relative characterization indicates that the introduction of the organic film can promote carrier transfer and charge collection, facilitating efficient photocurrent generation. This new device design strategy opens up a new window in developing low-cost sensitive NIR narrowband detection.

Unraveling Size-Dependent Ion-Migration for Stable Mixed-Halide Perovskite Light-Emitting Diodes.

Mixed-halide perovskites show tunable emission wavelength across the visible-light range, with optimum control of the light color. However, color stability remains limited due to the notorious halide segregation under illumination or an electric field. Here, a versatile path toward high-quality mixed-halide perovskites with high emission properties and resistance to halide segregation is presented. Through systematic in and ex situ characterizations, key features for this advancement are proposed: a slowed and controllable crystallization process can promote achievement of halide homogeneity, which in turn ensures thermodynamic stability; meanwhile, downsizing perovskite nanoparticle to nanometer-scale dimensions can enhance their resistance to external stimuli, strengthening the phase stability. Leveraging this strategy, devices are developed based on CsPbCl1.5 Br1.5 perovskite that achieves a champion external quantum efficiency (EQE) of 9.8% at 464 nm, making it one of the most efficient deep-blue mixed-halide perovskite light-emitting diodes (PeLEDs) to date. Particularly, the device demonstrates excellent spectral stability, maintaining a constant emission profile and position for over 60 min of continuous operation. The versatility of this approach with CsPbBr1.5 I1.5 PeLEDs is further showcased, achieving an impressive EQE of 12.7% at 576 nm.

High-fidelity and clean nanotransfer lithography using structure-embedded and electrostatic-adhesive carriers.

Metallic nanostructures are becoming increasingly important for both fundamental research and practical devices. Many emerging applications employing metallic nanostructures often involve unconventional substrates that are flexible or nonplanar, making direct lithographic fabrication very difficult. An alternative approach is to transfer prefabricated structures from a conventional substrate; however, it is still challenging to maintain high fidelity and a high yield in the transfer process. In this paper, we propose a high-fidelity, clean nanotransfer lithography method that addresses the above challenges by employing a polyvinyl acetate (PVA) film as the transferring carrier and promoting electrostatic adhesion through triboelectric charging. The PVA film embeds the transferred metallic nanostructures and maintains their spacing with a remarkably low variation of <1%. When separating the PVA film from the donor substrate, electrostatic charges are generated due to triboelectric charging and facilitate adhesion to the receiver substrate, resulting in a high large-area transfer yield of up to 99.93%. We successfully transferred the metallic structures of a variety of materials (Au, Cu, Pd, etc.) with different geometries with a <50-nm spacing, high aspect ratio (>2), and complex 3D structures. Moreover, the thin and flexible carrier film enables transfer on highly curved surfaces, such as a single-mode optical fiber with a curvature radius of 62.5 µm. With this strategy, we demonstrate the transfer of metallic nanostructures for a compact spectrometer with Cu nanogratings transferred on a convex lens and for surface-enhanced Raman spectroscopy (SERS) characterization on graphene with reliable responsiveness.

Electrochemical Replication and Transfer for Low-Cost, Sub-100 nm Patterning of Materials on Flexible Substrates.

The fabrication of high-resolution patterns on flexible substrates is an essential step in the development of flexible electronics. However, the patterning process on flexible substrates often requires expensive equipment and tedious lithographic processing. Here, a bottom-up patterning technique, termed electrochemical replication and transfer (ERT) is reported, which fabricates multiscale patterns of a wide variety of materials by selective electrodeposition of target materials on a predefined template, and subsequent transfer of the electrodeposited materials to a flexible substrate, while leaving the undamaged template for reuse for over 100 times. The additive and parallel patterning attribute of ERT allows the fabrication of multiscale patterns with resolutions spanning from sub-100 nm to many centimeters simultaneously, which overcomes the trade-off between resolution and throughput of conventional patterning techniques. ERT is suitable for fabricating a wide variety of materials including metals, semiconductors, metal oxides, and polymers into arbitrary shapes on flexible substrates at a very low cost.

Hybrid modeling of perovskite light-emitting diodes with nanostructured emissive layers.

Perovskite light-emitting diodes (PeLEDs) have attracted much attention due to their superior performance. When a bottleneck of energy conversion efficiency is achieved with materials engineering, nanostructure incorporation proves to be a feasible approach to further improve device efficiencies via light extraction enhancement. The finite-difference time-domain simulation is widely used for optical analysis of nanostructured optoelectronic devices, but reliable modeling of PeLEDs with nanostructured emissive layers remains unmet due to the difficulty of locating dipole light sources. Herein we established a hybrid process for modeling light emission behaviors of such nanostructured PeLEDs by calibrating light source distribution through electrical simulations. This hybrid modeling method serves as a universal tool for structure optimization of light-emitting diodes with nanostructured emissive layers.

Spatial modulation of nanopattern dimensions by combining interference lithography and grayscale-patterned secondary exposure.

Functional nanostructures are exploited for a variety of cutting-edge fields including plasmonics, metasurfaces, and biosensors, just to name a few. Some applications require nanostructures with uniform feature sizes while others rely on spatially varying morphologies. However, fine manipulation of the feature size over a large area remains a substantial challenge because mainstream approaches to precise nanopatterning are based on low-throughput pixel-by-pixel processing, such as those utilizing focused beams of photons, electrons, or ions. In this work, we provide a solution toward wafer-scale, arbitrary modulation of feature size distribution by introducing a lithographic portfolio combining interference lithography (IL) and grayscale-patterned secondary exposure (SE). Employed after the high-throughput IL, a SE with patterned intensity distribution spatially modulates the dimensions of photoresist nanostructures. Based on this approach, we successfully fabricated 4-inch wafer-scale nanogratings with uniform linewidths of <5% variation, using grayscale-patterned SE to compensate for the linewidth difference caused by the Gaussian distribution of the laser beams in the IL. Besides, we also demonstrated a wafer-scale structural color painting by spatially modulating the filling ratio to achieve gradient grayscale color using SE.

Ultrasensitive Molecular Detection by Imaging of Centimeter-Scale Metasurfaces with a Deterministic Gradient Geometry.

Highly sensitive detection of trace amounts of substances is crucial for broad applications in healthcare, environmental monitoring, antiterrorism, etc., where cost effectiveness and portability are often demanded. Here, an ultrasensitive sensor is reported that can detect an angstrom-thick layer of adsorbed molecules through image acquisition and processing. The sensor features a centimeter-scale plasmonic metasurface with spatially varying geometry, where the light scattering is dependent on both the adsorbed substances and spatial locations. When illuminated with narrowband light (such as from a light emitting diode), the intensity pattern recorded on the metasurface changes with the surface-adsorbed molecules, enabling label-free, sensitive, and spectrometer-free molecular detection. The centimeter-scale size of the sensing area interfaces well with consumer-level imaging sensors on mobile devices without the need for microscopic optics and offers a high signal-to-noise ratio by leveraging the multimillion pixels for noise reduction. It is experimentally demonstrated that a single layer of Al2 O3 molecules deposited on the sensor, with a thickness of approximately one angstrom, can be detected by analyzing the images taken of the sensing chip. Furthermore, by integrating the sensor into a microfluidic setup, quantitative detection of BSA/anti-BSA immune complex formation events is demonstrated, which agrees well with the Langmuir isotherm model.

On-Demand 3D Printing of Nanowire Probes for High-Aspect-Ratio Atomic Force Microscopy Imaging.

With the growing importance of three-dimensional (3D) nanomaterials and devices, there has been a great demand for high-fidelity, full profile topographic characterizations in a nondestructive manner. A promising route is to employ a high-aspect-ratio (HAR) probe in atomic force microscopy (AFM) imaging. However, the fabrication of HAR-AFM probes continues to suffer from extravagant cost, limited material choice, and complicated manufacturing steps. Here, we report one-step, on-demand electrohydrodynamic 3D printing of metallic HAR-AFM probes with tailored dimensions. Our additive fabrication approach yields a freestanding metallic nanowire with an aspect ratio over 30 directly on a cantilever within tens of seconds, producing a HAR-AFM probe. Furthermore, the benefits associated with unprecedented simplicity in the probe's dimension control, material selection, and regeneration are provided. The 3D-printed HAR-AFM probe exhibits a better fidelity in deep trench AFM imaging than a standard pyramidal probe. We expect this approach to find facile, material-saving manufacturing routes in particular for customizing functional nanoprobes.

Gradient wettability induced by deterministically patterned nanostructures.

We report a large-scale surface with continuously varying wettability induced by ordered gradient nanostructures. The gradient pattern is generated from nonuniform interference lithography by utilizing the Gaussian-shaped intensity distribution of two coherent laser beams. We also develop a facile fabrication method to directly transfer a photoresist pattern into an ultraviolet (UV)-cured high-strength replication molding material, which eliminates the need for high-cost reactive ion etching and e-beam evaporation during the mold fabrication process. This facile mold is then used for the reproducible production of surfaces with gradient wettability using thermal-nanoimprint lithography (NIL). In addition, the wetting behavior of water droplets on the surface with the gradient nanostructures and therefore gradient wettability is investigated. A hybrid wetting model is proposed and theoretically captures the contact angle measurement results, shedding light on the wetting behavior of a liquid on structures patterned at the nanoscale.

A Bilayer 2D-WS2/Organic-Based Heterojunction for High-Performance Photodetectors.

Two-dimensional (2D) tungsten disulfide (WS2) has inspired great efforts in optoelectronics, such as in solar cells, light-emitting diodes, and photodetectors. However, chemical vapor deposition (CVD) grown 2D WS2 domains with the coexistence of a discontinuous single layer and multilayers are still not suitable for the fabrication of photodetectors on a large scale. An emerging field in the integration of organic materials with 2D materials offers the advantages of molecular diversity and flexibility to provide an exciting aspect on high-performance device applications. Herein, we fabricated a photodetector based on a 2D-WS2/organic semiconductor materials (mixture of the (Poly-(N, N'-bis-4-butylphenyl-N, N'-bisphenyl) benzidine and Phenyl-C61-butyric acid methyl ester (Poly-TPD/PCBM)) heterojunction. The application of Poly-TPD/PCBM organic blend film enhanced light absorption, electrically connected the isolated WS2 domains, and promoted the separation of electron-hole pairs. The generated exciton could sufficiently diffuse to the interface of the WS2 and the organic blend layers for efficient charge separation, where Poly-TPD was favorable for hole carrier transport and PCBM for electron transport to their respective electrodes. We show that the photodetector exhibited high responsivity, detectivity, and an on/off ratio of 0.1 A/W, 1.1 × 1011 Jones, and 100, respectively. In addition, the photodetector showed a broad spectral response from 500 nm to 750 nm, with a peak external quantum efficiency (EQE) of 8%. Our work offers a facile solution-coating process combined with a CVD technique to prepare an inorganic/organic heterojunction photodetector with high performance on silicon substrate.

Selective Electroless Metallization of Micro- and Nanopatterns via Poly(dopamine) Modification and Palladium Nanoparticle Catalysis for Flexible and Stretchable Electronic Applications.

The authors report a new patterned electroless metallization process for creating micro- and nanoscale metallic structures on polymeric substrates, which are essential for emerging flexible and stretchable optical and electronic applications. This novel process features a selective adsorption of catalytic Pd nanoparticles (PdNPs) on a lithographically masked poly(dopamine) (PDA) interlayer in situ polymerized on the substrates. The moisture-resistant PDA layer has excellent stability under a harsh electroless plating bath, which enables electroless metallization on versatile substrate materials regardless of their hydrophobicity, and significantly strengthens the attachment of electroless plated metallic structures on the polymeric substrates. Prototype devices fabricated using this PDA-assisted electroless metallization patterning exhibit superior mechanical stability under high bending and stretching stress. The lithographic patterning of the PDA spatially confines the adsorption of PdNPs and reduces defects due to random adsorption of catalytic particles on the undesired area. The high resolution of the lithographic patterning enables the demonstration of a copper micrograting pattern with a linewidth down to 2 µm and a silver plasmonic nanodisk array with a 500 nm pitch. A copper mesh is also fabricated using our new patterned electroless metallization process and functions as flexible transparent electrodes with >80% visible transmittance and <1 Ω sq-1 sheet resistance. Moreover, flexible and stretchable dynamic electroluminescent displays and functional flexible printed circuits are demonstrated to show the promising capability of our fabrication process in versatile flexible and stretchable electronic devices.

Top-down fabrication of shape-controlled, monodisperse nanoparticles for biomedical applications.

Nanoparticles for biomedical applications are generally formed by bottom-up approaches such as self-assembly, emulsification and precipitation. But these methods usually have critical limitations in fabrication of nanoparticles with controllable morphologies and monodispersed size. Compared with bottom-up methods, top-down nanofabrication techniques offer advantages of high fidelity and high controllability. This review focuses on top-down nanofabrication techniques for engineering particles along with their biomedical applications. We present several commonly used top-down nanofabrication techniques that have the potential to fabricate nanoparticles, including photolithography, interference lithography, electron beam lithography, mold-based lithography (nanoimprint lithography and soft lithography), nanostencil lithography, and nanosphere lithography. Varieties of current and emerging applications are also covered: (i) targeting, (ii) drug and gene delivery, (iii) imaging, and (iv) therapy. Finally, a future perspective of the nanoparticles fabricated by the top-down techniques in biomedicine is also addressed.

Stretchable Transparent Electrodes with Solution-Processed Regular Metal Mesh for an Electroluminescent Light-Emitting Film.

We report stretchable metal-mesh transparent electrodes (TEs) with excellent electrical conductivity (<2 Ω/sq) and optical transparency (>80%) under up to 55% strain. The figures of merit on these electrodes, as defined as the ratio between electrical conductivity and optical conductivity, are among the highest reported for stretchable TEs under moderate stretching. Moreover, we demonstrate their application in a stretchable electroluminescent (EL) light-emitting film as top and bottom electrodes. EL lighting devices require low-resistance electrodes to unleash their potential for large-area low-power-consumption applications, in which our highly conductive and transparent stretchable TEs provide an edge on other competitor approaches. Importantly, our stretchable metal-mesh electrodes are fabricated through a vacuum-free solution-processed approach that is scalable for cost-effective mass production. We also investigate the fracture and fatigue mechanisms of stretchable metal-mesh electrodes with various mesh patterns and observe different behaviors under one-time and cyclic stretching conditions. Our solution-processed fabrication method, failure mechanism investigation, and device demonstration for metal-mesh stretchable TEs will facilitate the adoption of this promising high-performance approach in stretchable and wearable electronics applications.

Wafer-scale nanopatterning using fast-reconfigurable and actively-stabilized two-beam fiber-optic interference lithography.

A fast-reconfigurable and actively-stabilized fiber-optic interference lithography system is demonstrated in this paper. Employment of fiber-optic components greatly enhances the flexibility of the whole system, simplifies its optical alignment, and suppresses the interference of mechanical vibrations. Active stabilization is implemented in the system and evaluated through modeling and experiment. We demonstrate 3-inch-diameter wafer-scale patterning of 240-nm-period grating lines with a sub-50-nm linewidth and an aspect ratio over 3. Two-dimensional patterns of different geometries and dimensions are also demonstrated to show the versatility of our system. Step-and-repeat exposure is demonstrated with independently controlled patterning fields of 2×2cm2 large.

Bioinspired Nanostructured Surfaces for On-Demand Bubble Transportation.

The maneuver of small bubbles in a programmed way will advance numerous processes, including gas evolution reaction and aeration. Unlike in-air droplets, rapidly rising bubbles in liquid medium can hardly be steered through interaction with solid substrates, causing difficulties in maneuvering bubbles. We pattern and lubricate nanoporous substrates with regions of contrasting wettability that is similar to the back of Namib desert beetles and subsequently immerse the lubricated surface underwater to spontaneously form spatially patterned Nepenthes-inspired slippery surfaces after the dewetting of lubricants. As a result, bubbles are confined on lubricant-infused surfaces, with their high mobility well preserved. The interfacial states of attached bubbles are analyzed, and their dynamic sliding velocities are quantified. Using the lubricated patterned surfaces, we further demonstrate the predefined motion of bubbles driven by buoyancy at a small tiling angle, as well as a self-propulsion of bubbles driven by surface tension force at a tilting angle of 0°, respectively. The spatially lubricated surfaces simplify gas handling in liquid medium and have potential applications in fields where bubble handling is crucial.

Light-stimulated actuators based on nickel hydroxide-oxyhydroxide.

Light-induced actuators that are self-contained and compact can be used as artificial muscles for microrobotics because their actuation can be induced wirelessly, which reduces the complexity of the device or system. Here, we report a material system, nickel hydroxide-oxyhydroxide, that could actuate because of a volume change stimulated by illumination of visible light of low intensities. The actuating material here exhibited a turbostratic crystal structure capable of intercalating water, and we show that the intercalated water can be rapidly and reversibly desorbed into the environment under visible light of low intensities, resulting in fast actuation driven wirelessly by light. By electroplating the actuating material on passive substrates, we have fabricated film actuators capable of undergoing reversible bending and curling with an intrinsic actuating stress of 5 to 65 megapascals at response rates in the order of tens to hundreds of degrees per second depending on the light intensity, which are comparable to mammalian skeletal muscles. By intentionally electroplating the nickel hydroxide-oxyhydroxide on selected areas of the substrate, a hinged actuator that can lift objects ~100 times the weight of the actuating material is achieved. Other demonstrations show the potential uses in robotic devices, including sunlight-induced actuation, a biomimicked "sensitive plant" with rapid leaf movement, and a light-powered walking bot.

Highly transparent and flexible polyaniline mesh sensor for chemiresistive sensing of ammonia gas.

A new structure of a flexible, transparent polyaniline (PANI) ammonia gas sensor is reported. The sensor features a hierarchical nanostructured PANI polymer arranged in a micromesh, exhibiting excellent chemiresistive sensitivity to ammonia gas and near-neutral color transparency. The PANI mesh is embedded in a flexible substrate and therefore exhibits superior mechanical stability against peeling and bending. These merits make it a promising candidate for application in wearable electronics. Moreover, the PANI mesh sensor is fabricated through a cost-effective, solution-based strategy that enables vacuum-free fabrication of a sacrificial catalytic copper mesh followed by in situ polymerization, and this strategy is scalable for high-volume production. We demonstrate the high-performance resistive sensing of ammonia gas with concentrations from 2.5 ppb to 100 ppm using this flexible PANI mesh sensor with an excellent transparency of 88.4% at 600 nm wavelength. Furthermore, no significant degradation in the sensing performance occurs after 1000 bending cycles.