Progression in the Fountain Pen Approach: From 2D Writing to 3D Free‐Form Micro/Nanofabrication

The fountain pen approach, as a means for transferring materials to substrates, has shown numerous incarnations in recent years for creating 2D micro/nanopatterns and even generating 3D free‐form nanostructures using a variety of material “inks”. While the idea of filled reservoirs used to deliver material to a substrate via a capillary remains unchanged since antiquity, the advent of precise micromanipulation systems and functional material “inks” allows the extension of this mechanism to more high‐tech applications. Herein, the recent growth in meniscus guided fountain pen approaches for benchtop micro/nanofabrication, which has occurred in the last decade, is discussed. Particular attention is given to the theory, equipment, and experimentation encompassing this unique direct writing approach. A detailed exploration of the diverse ink systems and functional device applications borne from this strategy is put forth to reveal its rapid expansion to a broad range of scientific and engineering disciplines. As such, this informative review is provided for researchers considering adoption of this recent advancement of a familiar technology.     

High‐Performance Packaged 3D Lithium‐Ion Microbatteries Fabricated Using Imprint Lithography

Fabrication of high‐energy‐density and high‐power‐density packaged long‐cycle‐life rechargeable microbatteries remains a considerable challenge. Here, high‐performance microbatteries with high active volume fraction, thick, 3D‐structured electrodes (V₂O₅ cathode and Li metal anode) are realized through a combination of imprint lithography, self‐assembly, and electrodeposition. To assist the critical challenge of hermetic packaging, the microbattery is infilled with a gel electrolyte. The packaged cell exhibits high areal energy and power densities of 1.24 J cm^?2 and 75.5 mW cm^?2, respectively, and can be cycled 550 times in argon or 200 times in air with 75% capacity retention of the initial discharge capacity. An unpackaged cell, using a liquid electrolyte, provides a power density of 218 mW cm^?2. As far as it is known, the microbatteries have the highest peak power density among all reported microbatteries.     

Near‐Infrared Light‐Sensitive Polyvinyl Alcohol Hydrogel Photoresist for Spatiotemporal Control of Cell‐Instructive 3D Microenvironments

Advanced hydrogel systems that allow precise control of cells and their 3D microenvironments are needed in tissue engineering, disease modeling, and drug screening. Multiphoton lithography (MPL) allows true 3D microfabrication of complex objects, but its biological application requires a cell‐compatible hydrogel resist that is sufficiently photosensitive, cell‐degradable, and permissive to support 3D cell growth. Here, an extremely photosensitive cell‐responsive hydrogel composed of peptide‐crosslinked polyvinyl alcohol (PVA) is designed to expand the biological applications of MPL. PVA hydrogels are formed rapidly by ultraviolet light within 1 min in the presence of cells, providing fully synthetic matrices that are instructive for cell‐matrix remodeling, multicellular morphogenesis, and protease‐mediated cell invasion. By focusing a multiphoton laser into a cell‐laden PVA hydrogel, cell‐instructive extracellular cues are site‐specifically attached to the PVA matrix. Cell invasion is thus precisely guided in 3D with micrometer‐scale spatial resolution. This robust hydrogel enables, for the first time, ultrafast MPL of cell‐responsive synthetic matrices at writing speeds up to 50 mm s^?1. This approach should enable facile photochemical construction and manipulation of 3D cellular microenvironments with unprecedented flexibility and precision.     

Patterned Arrays of Functional Lateral Heterostructures via Sequential Template‐Directed Printing

The precise integration of microscale dots and lines with controllable interfacing connections is highly important for the fabrication of functional devices. To date, the solution‐processible methods are used to fabricate the heterogeneous micropatterns for different materials. However, for increasingly miniaturized and multifunctional devices, it is extremely challenging to engineer the uncertain kinetics of a solution on the microstructures surfaces, resulting in uncontrollable interface connections and poor device performance. Here, a sequential template‐directed printing process is demonstrated for the fabrication of arrayed microdots connected by microwires through the regulation of the Rayleigh–Taylor instability of material solution or suspension. Flexibility in the control of fluidic behaviors can realize precise interface connection between the micropatterns, including the microwires traversing, overlapping or connecting the microdots. Moreover, various morphologies such as circular, rhombic, or star‐shaped microdots as well as straight, broken or curved microwires can be achieved. The lateral heterostructure printed with two different quantum dots displays bright dichromatic photoluminescence. The ammonia gas sensor printed by polyaniline and silver nanoparticles exhibits a rapid response time. This strategy can construct heterostructures in a facile manner by eliminating the uncertainty of the multimaterials interface connection, which will be promising for the development of novel lateral functional devices.     

Atomic‐Level Sculpting of Crystalline Oxides: Toward Bulk Nanofabrication with Single Atomic Plane Precision

The atomic‐level sculpting of 3D crystalline oxide nanostructures from metastable amorphous films in a scanning transmission electron microscope (STEM) is demonstrated. Strontium titanate nanostructures grow epitaxially from the crystalline substrate following the beam path. This method can be used for fabricating crystalline structures as small as 1–2 nm and the process can be observed in situ with atomic resolution. The fabrication of arbitrary shape structures via control of the position and scan speed of the electron beam is further demonstrated. Combined with broad availability of the atomic resolved electron microscopy platforms, these observations suggest the feasibility of large scale implementation of bulk atomic‐level fabrication as a new enabling tool of nanoscience and technology, providing a bottom‐up, atomic‐level complement to 3D printing.     

3D Nanofabrication of Fluidic Components by Corner Lithography

A reproducible wafer‐scale method to obtain 3D nanostructures is investigated. This method, called corner lithography, explores the conformal deposition and the subsequent timed isotropic etching of a thin film in a 3D shaped silicon template. The technique leaves a residue of the thin film in sharp concave corners which can be used as structural material or as an inversion mask in subsequent steps. The potential of corner lithography is studied by fabrication of functional 3D microfluidic components, in particular i) novel tips containing nano‐apertures at or near the apex for AFM‐based liquid deposition devices, and ii) a novel particle or cell trapping device using an array of nanowire frames. The use of these arrays of nanowire cages for capturing single primary bovine chondrocytes by a droplet seeding method is successfully demonstrated, and changes in phenotype are observed over time, while retaining them in a well‐defined pattern and 3D microenvironment in a flat array.     

Highly Efficient 2D/3D Hybrid Perovskite Solar Cells via Low‐Pressure Vapor‐Assisted Solution Process

The fabrication of multidimensional organometallic halide perovskite via a low‐pressure vapor‐assisted solution process is demonstrated for the first time. Phenyl ethyl‐ammonium iodide (PEAI)‐doped lead iodide (PbI₂) is first spin‐coated onto the substrate and subsequently reacts with methyl‐ammonium iodide (MAI) vapor in a low‐pressure heating oven. The doping ratio of PEAI in MAI‐vapor‐treated perovskite has significant impact on the crystalline structure, surface morphology, grain size, UV–vis absorption and photoluminescence spectra, and the resultant device performance. Multiple photoluminescence spectra are observed in the perovskite film starting with high PEAI/PbI₂ ratio, which suggests the coexistence of low‐dimensional perovskite (PEA₂MA_n?1Pb_nI_3n+1) with various values of n after vapor reaction. The dimensionality of the as‐fabricated perovskite film reveals an evolution from 2D, hybrid 2D/3D to 3D structure when the doping level of PEAI/PbI₂ ratio varies from 2 to 0. Scanning electron microscopy images and Kelvin probe force microscopy mapping show that the PEAI‐containing perovskite grain is presumably formed around the MAPbI₃ perovskite grain to benefit MAPbI₃ grain growth. The device employing perovskite with PEAI/PbI₂ = 0.05 achieves a champion power conversion efficiency of 19.10% with an open‐circuit voltage of 1.08 V, a current density of 21.91 mA cm^?2, and a remarkable fill factor of 80.36%.     

4D Biofabrication Using Shape‐Morphing Hydrogels

Despite the tremendous potential of bioprinting techniques toward the fabrication of highly complex biological structures and the flourishing progress in 3D bioprinting, the most critical challenge of the current approaches is the printing of hollow tubular structures. In this work, an advanced 4D biofabrication approach, based on printing of shape‐morphing biopolymer hydrogels, is developed for the fabrication of hollow self‐folding tubes with unprecedented control over their diameters and architectures at high resolution. The versatility of the approach is demonstrated by employing two different biopolymers (alginate and hyaluronic acid) and mouse bone marrow stromal cells. Harnessing the printing and postprinting parameters allows attaining average internal tube diameters as low as 20 µm, which is not yet achievable by other existing bioprinting/biofabrication approaches and is comparable to the diameters of the smallest blood vessels. The proposed 4D biofabrication process does not pose any negative effect on the viability of the printed cells, and the self‐folded hydrogel‐based tubes support cell survival for at least 7 d without any decrease in cell viability. Consequently, the presented 4D biofabrication strategy allows the production of dynamically reconfigurable architectures with tunable functionality and responsiveness, governed by the selection of suitable materials and cells.