Facile Fabrication of Ordered Crystalline‐Semiconductor Microstructures on Compliant Substrates

Buckling and wrinkling of thin films on a compliant material has proved to be a resource in several applications, such as flexible electronics, thin‐film metrology and fabrication of tunable optical components. A versatile approach for the fabrication of two‐dimensional and linear arrays of buckled structures is demonstrated here using a stiff material, in the form of a nanomembrane, on a compliant substrate. The novelty of the fabrication process is that the substrates are strained by isotropic volume expansion in solvents. This work illustrates in detail the potential of our technology to fabricate ordered arrays of 3D structures on large‐area compliant substrates, with important implications for a large number of fields. Furthermore, this paper discusses the interesting interface chemistry and mechanics leading to controllable and reproducible fabrication of our 3D structures.     

Tunable Band‐Selective UV‐Photodetectors by 3D Self‐Assembly of Heterogeneous Nanoparticle Networks

Accurate detection of ultraviolet radiation is critical to many technologies including wearable devices for skin cancer prevention, optical communication systems, and missile launch detection. Here, a nanoscale architecture is presented for band‐selective UV‐photodetectors, which features unique tunability and miniaturization potential. The device layout relies on the 3D integration of ultraporous layers of tailored nanoparticles. By tailoring the transmittance window between the indirect band gap of TiO₂ nanoparticles and the sharp edge of the direct band gap of ZnO, a band‐selective photoresponse is achieved with tunable bandwidth to less than 30 nm and photo‐ to dark‐current ratios of several millions at a light intensity of 86 μW cm^?2 and operation bias of 1 V. The potential of this integrated morphology is shown by fabrication of the first inherent UVA photodetector with selectivity against the edge of the UVB and visible light of nearly 60 times. This tunable architecture and nanofabrication approach are compatible with state‐of‐the micromachining technologies and provide a flexible solution for the engineering of wearable band‐selective photodetectors.     

Locally and Dynamically Controllable Surface Topography Through the Use of Particle‐Enhanced Soft Composites

A new class of soft composite materials with dynamically tunable and reversible surface topographies is introduced that allows a wide diversity and local positioning of surface features. The particle‐enhanced soft composites are comprised of a soft elastomeric matrix with relatively stiff particles embedded below the surface. Upon application of external stimuli, a surface that is originally smooth and flat (or of other initial topology) transforms to engineered surface topographies. Finite element based micromechanical simulations are used to design and study the hybrid material structures that govern the evolution in surface topographies. Physical prototypes are fabricated using multimaterial 3D‐printing, and then experimentally evaluated to validate the accuracy of our simulations. It is demonstrated that a rich variety in periodic and random surface features including variable waves, crease‐like features, flat apexes, and valleys can be attained by changing different dimensionless geometric parameters (e.g., relative particle size, shapes, spacing, and distributions). Furthermore, these surface features can be locally controlled by positioning of particles and do not rely on instabilities. The material design depends primarily on the geometry of the particles and the arrays, making this approach to on‐demand custom and reversible surface patterning applicable over a wide range of size scales.     

One‐Pot Synthesis of Freestanding Porous Palladium Nanosheets as Highly Efficient Electrocatalysts for Formic Acid Oxidation

Freestanding ultrathin 2D noble metal nanosheets have drawn enormous attention due to their potential applications in various fields. However, the synthesis of 2D noble metal nanosheets still remains a great challenge due to the lack of an intrinsic driving force for anisotropic growth of 2D structures. Here, a facile one‐pot synthesis of ultrathin freestanding porous Pd nanosheets (≈2.5 µm in lateral size and 10 nm in thickness) flexibly knitted by interweaved ultrathin nanowires with the assistance of poly(diallyldimethylammonium chloride) is presented. Nanoparticles attachment and subsequent self‐assembly in the synthetic process are responsible for the formation of such intriguing nanostructures. Moreover, finely controlling the pH value of the precursor solution leads to yield different Pd nanostructures with tunable dimensionalities, including 3D nanoflowers, 2D nanosheets, and 1D nanochains. Owing to the unique structural features, the obtained freestanding porous Pd nanosheets exhibit excellent electrocatalytic activity and stability towards formic acid oxidation compared to those of other dimensional counterparts and commercial Pd black.     

Fabrication of Ordered Nanostructured Arrays Using Poly(dimethylsiloxane) Replica Molds Based on Three‐Dimensional Colloidal Crystals

Hexagonally arrayed structures of colloidal crystals with uniform surface are a good candidate for master molds to be used in soft lithography. Here, the fabrication of periodically arrayed nanostructures using poly(dimethylsiloxane) (PDMS) molds based on three‐dimensionally (3D) ordered colloidal crystals is reported. A robust, high‐quality 3D colloidal‐crystal master molds is prepared using the colloidal suspension containing a water‐soluble polymer. The surface patterns of the 3D colloidal crystals can then be transferred onto a polymer film via soft lithography, by means of the replication of the surface pattern with PDMS. Various hexagonally arrayed nanostructure patterns can be fabricated, including close‐packed and non‐close‐packed 2D arrays and honeycomb structures by the structural modification of the 3D colloidal‐crystal templates. The replicated hexagonally arrayed structures can also be used as templates for producing colloidal crystals with 2D superlattices.     

Tunable Synthesis of Various Wurtzite ZnS Architectural Structures and Their Photocatalytic Properties

Semiconductor ZnS with novel and complex 3D architectures such as nanorods (or nanowires) networks, urchinlike nanosturctures, nearly monodisperse nanospheres self‐assembled from nanorods and 1D nanostructures (rods and wires) had been synthesized in a binary solution by controlling the reaction conditions, such as the volume ratio of the mixed solvents and the reaction temperature. The morphology of ZnS changed from 3D architectural structures to 1D rodlike (or wirelike) shape when the temperature was increased from 160 to 200–240 °C. The possible growth mechanisms for the formation of nanospheres self‐assembled from nanorods are tentatively discussed according to the experimental results. The photocatalytic activity of various ZnS nanostructures has been tested by degradation of acid fuchsine under infrared light compared to that of commercial ZnS powders under infrared‐light irradiation and commercial TiO₂ powders under UV‐light irradiation, indicating that the as‐obtained ZnS nanostructures exhibit excellent photocatalytic activity for degradation of acid fuchsine.     

Electrochemical and Top‐Down 3D Ion‐Carving to Change Magnetic Properties

It is challenging to develop new top‐down approaches to tailor particles into subnanometer size structures on a large scale to further reveal their structure‐dependent physicochemical properties. Here, we demonstrate a non‐conventional, electrochemical, 3D ion‐carving process to tailor particles into subscale flower‐like nanostructures at room temperature. The technology is based on the electrochemical insertion/extraction of lithium ions as a carving “knife” to carve the single‐crystalline particle precursor into higher‐order, flower‐like nanostructures with hexagonal nanopetals as the building units. Our study demonstrates that the morphology of the as‐carved, flower‐like nanostructures can be controlled by the electrochemical parameters, such as the current density and the number of cycles. Particularly interesting is that dramatically different magnetic properties can be achieved depending on the morphology through careful tuning by the electrochemical ion‐carving process. The as‐carved, flower‐like particles may find many important applications, including magnetic nanodevices. Our approach, in principle, is applicable to prepare various kinds of 3D‐structured materials with different compositions.     

Simple Holographic Patterning for High‐Aspect‐Ratio Three‐Dimensional Nanostructures with Large Coverage Area

Using the vertical standing wave phenomena commonly regarded as a deterrent in holographic lithography, multifaceted three‐dimensional (3D) nanostructures are fabricated on polymeric photoresist materials using a simple two‐beam interferometer. Large‐area 3D nanostructures with high aspect ratios (greater than 10) are readily produced using this methodology, including grating, pillar and pore patterns. Furthermore, manipulation of the lithography process conditions results in unique sidewall profiles of the nanostructures. Such 3D holographic control even produces highly porous polymer membranes composed of 3D interconnected pore networks, which resembles the 3D photonic crystal compound nanostructures that were previously attainable only with limited pattern coverage area using complex multibeam holographic lithography processes. Such well‐tailored high‐aspect‐ratio 3D nanostructures with large pattern coverage area further enable the fabrication of novel nanostructures for functionalized materials via various additive and subtractive pattern transfer techniques such as etching, deposition, and molding. In particular, direct molding followed by thermal decomposition process leads to the synthesis of hierarchical titanium oxide nanostructures of tunable 3D geometry, which would be of great significance in applications of photonic crystals, photovoltaic solar cells, and photocatalyst in water decontamination.     

Tuning the Porosity of Bimetallic Nanostructures by a Soft Templating Approach

Hexagonal mesophases made of oil‐swollen surfactant‐stabilized tubes arranged on a triangular lattice in water and doped with metallic salts are used as templates for the radiolytic synthesis of nanostructures. The nanostructures formed in this type of soft matrix are bimetallic palladium‐platinum porous nanoballs composed of 3D‐connected nanowires, of typical thickness 2.5 nm, forming hexagonal cells. Using electron microscopy and small‐angle X‐ray scattering it is demonstrated that the pore size of the nanoballs is directly determined by the diameter of the oil tube of the doped mesophases, which is varied in a controlled fashion from 10 to 55 nm. Bimetallic nanostructures composed of various proportions of palladium and platinum can be synthesized. Their alloy structure is studied using X‐ray photoelectron spectroscopy, energy‐dispersive X‐ray spectroscopy, and high‐angular dark field scanning transmission electron microscopy experiments. The templating approach allows the synthesis of bimetallic nanoballs of tunable porosity and composition.     

Constrained Order in Nanoporous Alumina with High Aspect Ratio: Smart Combination of Interference Lithography and Hard Anodization

With only two matched processing steps, the fabrication of thick nanoporous alumina membranes with mono‐oriented, perfect hexagonal packing of pores, and precise control of all structural parameters over large areas is demonstrated. The cylindrical pores are uniform in shape and widely tunable in their dimensions and spatial distribution, with aspect ratios as high as 500. In brief, electropolished aluminum is first patterned using three‐beam interference lithography in a single step and then anodized in a hard regime. The periodic concavities in the aluminum surface guide the pore nucleation, and the self‐ordering phenomenon guarantees the maintenance of the predefined arrangement throughout the entire layer. In contrast to other methods, the interpore distance can be easily adjusted, the porous layer is not limited in thickness, no prefabricated stamps are involved, and the periodic pattern can be easily reproduced without risk of degradation. The approach overcomes the time, cost, and scale limitations of other existing processes. These membranes are well‐suited for the templated fabrication of perfectly ordered arrays of highly uniform 1D nanostructures. Thus, the application fields of these functional membranes are diverse: magneto‐optical and opto‐electronic devices, photonic crystals, solar cells, fuel cells, and chemical and biochemical sensing systems, to name a few.     

Inherent Photodegradability of Polymethacrylate Hydrogels: Straightforward Access to Biocompatible Soft Microstructures

Hydrogels are important functional materials useful for 3D cell culture, tissue engineering, 3D printing, drug delivery, sensors, or soft robotics. The ability to shape hydrogels into defined 3D structures, patterns, or particles is crucial for biomedical applications. Here, the rapid photodegradability of commonly used polymethacrylate hydrogels is demonstrated without the need to incorporate additional photolabile functionalities. Hydrogel degradation depths are quantified with respect to the irradiation time, light intensity, and chemical composition. It can be shown that these parameters can be utilized to control the photodegradation behavior of polymethacrylate hydrogels. The photodegradation kinetics, the change in mechanical properties of polymethacrylate hydrogels upon UV irradiation, as well as the photodegradation products are investigated. This approach is then exploited for microstructuring and patterning of hydrogels including hydrogel gradients as well as for the formation of hydrogel particles and hydrogel arrays of well‐defined shapes. Cell repellent but biocompatible hydrogel microwells are fabricated using this method and used to form arrays of cell spheroids. As this method is based on readily available and commonly used methacrylates and can be conducted using cheap UV light sources, it has vast potential to be applied by laboratories with various backgrounds and for diverse applications.     

Profile Control in Block Copolymer Nanostructures using Bilayer Thin Films for Enhanced Pattern Transfer Processes

Although control over the domain orientation and long‐range order of block copolymer nanostructures self‐assembled in thin films has been achieved using various directed self‐assembly techniques, more challenging but equally important for many lithographic applications is the ability to precisely control the shape of the interface between domains. Here, a novel layer‐by‐layer approach is reported for controlling the interface profile of block copolymer nanostructures and the application of an undercut sidewall profile for an enhanced metal lift‐off process for pattern transfer is demonstrated. Bilayer films of lamellar‐forming poly(styrene‐block‐methyl methacrylate) are assembled and thermally cross‐linked on wafer substrates in a layer‐by‐layer process. The top layer, while being directed to self‐assemble on the lamellae of the underlying layer, has a tunable composition and polystyrene domain width independent of that of the bottom layer. Undercut or negative sidewall profiles in the PS nanostructures are proven to provide better templates for the lift‐off of Au nanowires by achieving complete and defect‐free pattern transfer more than three times faster than comparable systems with vertical sidewall profiles. More broadly, the layer‐by‐layer approach presented here provides a pathway to achieving sophisticated interface profiles and user‐defined 3D block copolymer nanostructures in thin films.     

Elaborately Aligning Bead‐Shaped Nanowire Arrays Generated by a Superhydrophobic Micropillar Guiding Strategy

Bead‐shaped 1D structures are of great interest due to their unique applications in mesoscopic optics/electronics and their specific ability to collect tiny droplets. Here, a novel method to fabricate aligning bead‐shaped nanowire arrays assisted by highly adhesive superhydrophobic surfaces based on a micropillar guiding strategy is presented. Different from previous fabrication techniques, bead‐shaped nanowires generated in this method are strictly oriented in a large scale. Rayleigh instability, which occurs at ultralow polymer concentration, can introduce bead‐shaped nanowires at the cost of structural strength. Thus, PS spheres are more suitable to serve as bead building blocks to generate firm bead‐shaped nanowire arrays. The bead number is tunable by tailoring the polystyrene‐sphere/polyvinyl‐formal ratio. Furthermore, as‐prepared bead‐shaped nanowires have the unique ability to directionally drive tiny drops and collect coalesced microdroplets when placed in mist. With an increase in humidity, the nanowires show a segmented swelling behavior in the “bead” parts whereas the “joint nanowire” parts remain the same. Because such bead‐shaped nanowires are formed regularly, collected microdroplets upon the beads would not interact with each other. The findings offer new insight into the alignment of bead‐shaped nanostructures and might provide promising opportunities in fundamental research and for industrial applications.     

High‐Resolution Patterning of Various Large‐Area,Highly Ordered Structural Motifs by Directional Photofluidization Lithography: Sub‐30‐nm Line,Ellipsoid, Rectangle,and Circle Arrays

A major challenge in nanolithography is to overcome the resolution limit of conventional patterning methods. Herein, we demonstrate a simple and convenient approach to generate sub‐30‐nm various structural motifs with precisely controlled sizes, shapes, and orientations. The proposed method, the “directional photofluidization” of an azopolymer, follows the same philosophy as a path‐changing approach, for example, thermal‐reflow of polymer arrays, in that post‐treatment simultaneously leads to a reduction of the feature sizes and line‐edge roughness (LER) of nanostructures. However, in contrast to thermal‐induced isotropic reflow, directional photofluidization provides unprecedented flexibility to control the structural features, because the direction of photofluidization can be arbitrary controlled according to the light polarization. Furthermore, this approach offers good control of the final features due to a gradual reduction in the rate of photofluidization during light irradiation. More importantly, the photofluidic behavior of the azopolymer significantly reduces the LER, and thus it can improve the quality of nanostructures. Finally, the far‐field process of directional photofluidization enables hierarchical nanofabrication, in contrast to mechanical contact fabrication, because the patterned light can reconfigure the polymer arrays selectively. Our approach is potentially advantageous for the fabrication of various structural motifs with well‐controlled dimensions on the nanoscale and with minimized LER.     

A Three‐Dimensional Nanostructured Array of Protein Nanoparticles

Here a novel technique is reported to construct a three‐dimensional (3D) array of well‐defined and controllable multilayered nanostructures of proteins that is based on alternate layer‐by‐layer assembly of bacterial protein nanoparticles and DNA on a patterned array of gold dots. This is the first report on protein‐based multilayer stacking, which has the following significant advantages over conventional multilayer assemblies: 1) avoiding hazardous chemicals, the multilayer assembly is implemented in aqueous solution under mild temperature and pH conditions over a relatively short period; 2) direct multilayer growth from designated position is possible by controlling the aspect ratio; 3) multicomponent stacking can be easily performed through alternate stacking of different building blocks (in this case protein nanoparticles); and 4) a wide variety of 3D arrays can be constructed using various functionalized protein nanoparticles that are easily prepared through a simple genetic engineering approach. In this study, as a proof of concept, the developed 3D and patterned arrays of protein nanoparticle multilayers are successfully applied to the multiplexed bioassays of breast and colorectal cancer markers.     

Rapid Fabrication of Micro‐ and Nanoscale Patterns by Replica Molding from Diatom Biosilica

Diatoms are single‐celled micro‐algae that possess an exoskeleton (called frustule) comprised of diverse and highly ordered 3D porous silica structures and that hold considerable promise for biological or biomimetic fabrication of nanostructured materials and devices. We have used, for the first time, a soft lithographic approach of replica molding to replicate porous diatom structures into polymers. Two centric diatom species, Coscinodiscus sp., Thalassiosira eccentrica cultured in our laboratory were used as masters for replication. In the first step, replica molding onto soft and elastic polymer using poly(dimethylsiloxane) PDMS produced a negative replica of the diatom frustule. These PDMS replicas were then used as a mold to fabricate the positive polymer replicas of diatoms using a mercaptol ester type UV curable polymer (NOA 60). Fabricated polymer replicas were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). In all cases, diatom micro‐ and nanoscale porous structures were successfully transferred with high precision into polymer replicas. Such an accomplishment effectively demonstrates the potential for using diatoms as blueprints for rapid and simple fabrication of polymer nanostructures. The prepared replicas were used as diffraction gratings and as nanowells to hold polymeric nanoparticles effectively demonstrating the functional properties of these biomimetic structures.     

Highly Elastic,Transparent, and Conductive 3D‐Printed Ionic Composite Hydrogels

Despite extensive progress to engineer hydrogels for a broad range of technologies, practical applications have remained elusive due to their (until recently) poor mechanical properties and lack of fabrication approaches, which constrain active structures to simple geometries. This study demonstrates a family of ionic composite hydrogels with excellent mechanical properties that can be rapidly 3D‐printed at high resolution using commercial stereolithography technology. The new material design leverages the dynamic and reversible nature of ionic interactions present in the system with the reinforcement ability of nanoparticles. The composite hydrogels combine within a single platform tunable stiffness, toughness, extensibility, and resiliency behavior not reported previously in other engineered hydrogels. In addition to their excellent mechanical performance, the ionic composites exhibit fast gelling under near‐UV exposure, remarkable conductivity, and fast osmotically driven actuation. The design of such ionic composites, which combine a range of tunable properties and can be readily 3D‐printed into complex architectures, provides opportunities for a variety of practical applications such as artificial tissue, soft actuators, compliant conductors, and sensors for soft robotics.     

3D Free‐Form Patterning of Silicon by Ion Implantation,Silicon Deposition,and Selective Silicon Etching

A method for additive layer‐by‐layer fabrication of arbitrarily shaped 3D silicon micro‐ and nanostructures is reported. The fabrication is based on alternating steps of chemical vapor deposition of silicon and local implantation of gallium ions by focused ion beam (FIB) writing. In a final step, the defined 3D structures are formed by etching the silicon in potassium hydroxide (KOH), in which the local ion implantation provides the etching selectivity. The method is demonstrated by fabricating 3D structures made of two and three silicon layers, including suspended beams that are 40 nm thick, 500 nm wide, and 4 μm long, and patterned lines that are 33 nm wide.     

2D Material Enabled Offset‐Patterning with Atomic Resolution

Atomic‐precision patterning at large scale is a central requirement for nanotechnology and future electronics that is hindered by the limitations of lithographical techniques. Historically, imperfections of the fabrication tools have been compensated by multi‐patterning using sequential lithography processes. The realization of nanometer‐scale features from much larger patterns through offset stacking of atomically thin masks is demonstrated. A unique mutual stabilization effect between two graphene layers produces atomically abrupt transitions that selectively expose single‐layer covered regions. Bilayer regions, on the other hand, protect the underlying substrate from removal for several hours permitting transfer of atomic thickness variations into lateral features in various semiconductors. Nanoscopic offsets between two 2D materials layers could be introduced through bottom‐up and top‐down approaches, opening up new routes for high‐resolution patterning. A self‐aligned templating approach yields nanometer‐wide bilayer graphene nanoribbons with macroscopic length that produces high‐aspect‐ratio silicon nanowalls. Moreover, offset‐transfer of lithographically patterned graphene layers enables multipatterning of large arrays of semiconductor features whose resolution is not limited by the employed lithography and could reach <10 nm feature size. The results open up a new route to combining design flexibility with unprecedented resolution at large scale.     

Oriented Multiwalled Organic–Co(OH)2 Nanotubes for Energy Storage

In energy storage materials, large surface areas and oriented structures are key architecture design features for improving performance through enhanced electrolyte access and efficient electron conduction pathways. Layered hydroxides provide a tunable materials platform with opportunities for achieving such nanostructures via bottom‐up syntheses. These nanostructures, however, can degrade in the presence of the alkaline electrolytes required for their redox‐based energy storage. A layered Co(OH)₂–organic hybrid material that forms a hierarchical structure consisting of micrometer‐long, 30 nm diameter tubes with concentric curved layers of Co(OH)₂ and 1‐pyrenebutyric acid is reported. The nanotubular structure offers high surface area as well as macroscopic orientation perpendicular to the substrate for efficient electron transfer. Using a comparison with flat films of the same composition, it is demonstrated that the superior performance of the nanotubular films is the result of a large accessible surface area for redox activity. It is found that the organic molecules used to template nanotubular growth also impart stability to the hybrid when present in the alkaline environments necessary for redox function.