4D Printing of Ultrastretchable Magnetoactive Soft Material Architectures for Soft Actuators.

Magnetoactive soft materials (MSMs) comprising magnetic particles and soft matrices have emerged as smart materials for realizing soft actuators. 4D printing, which involves fabricating 3D architectures that can transform shapes under external magnetic fields, is an effective way to fabricate MSMs-based soft actuators with complex shapes. The printed MSMs must be flexible, stretchable, and adaptable in their magnetization profiles to maximize the degrees of freedom for shape morphing. This study utilizes a facile 4D printing strategy for producing ultrastretchable (stretchability > 1000%) MSM 3D architectures for soft-actuator applications. The strategy involves two sequential steps: (i) direct ink writing (DIW) of the MSM 3D architectures with ink composed of NdFeB and styrene-isoprene block copolymers (SIS) at room temperature and (ii) programming and reconfiguration of the magnetization profiles of the printed architecture using an origami-inspired magnetization method (magnetization field, Hm = 2.7 T). Various differently shaped MSM 3D architectures, which can be transformed into desired shapes under an actuation magnetic field (Ba = 85 mT), are successfully fabricated. In addition, two different soft-actuator applications are demonstrated: a multifinger magnetic soft gripper and a Kirigami-shaped 3D electrical switch with conductive and magnetic functionalities. Our strategy shows potential for realizing multifunctional, shape-morphing, and reprogrammable magnetoactive devices for advanced soft-actuator applications.

Three-Dimensional Printing of Structural Color Using a Femtoliter Meniscus.

Structural colors are produced by the diffraction of light from microstructures. The collective arrangement of substructures is a simple and cost-effective approach for structural coloration represented by colloidal self-assembly. Nanofabrication methods enable precise and flexible coloration by processing individual nanostructures, but these methods are expensive or complex. Direct integration of desired structural coloration remains difficult because of the limited resolution, material-specificity, or complexity. Here, we demonstrate three-dimensional printing of structural colors by direct writing of nanowire gratings using a femtoliter meniscus of polymer ink. This method combines a simple process, desired coloration, and direct integration at a low cost. Precise and flexible coloration is demonstrated by printing the desired structural colors and shapes. In addition, alignment-resolved selective reflection is shown for displayed image control and color synthesis. The direct integration facilitates structural coloration on various substrates, including quartz, silicon, platinum, gold, and flexible polymer films. We expect that our contribution can expand the utility of diffraction gratings across various disciplines such as surface-integrated strain sensors, transparent reflective displays, fiber-integrated spectrometers, anticounterfeiting, biological assays, and environmental sensors.

Meniscus-Guided Micro-Printing of Prussian Blue for Smart Electrochromic Display.

Using energy-saving electrochromic (EC) displays in smart devices for augmented reality makes cost-effective, easily producible, and efficiently operable devices for specific applications possible. Prussian blue (PB) is a metal-organic coordinated compound with unique EC properties that limit EC display applications due to the difficulty in PB micro-patterning. This work presents a novel micro-printing strategy for PB patterns using localized crystallization of FeFe(CN)6 on a substrate confined by the acidic-ferric-ferricyanide ink meniscus, followed by thermal reduction at 120 °C, thereby forming PB. Uniform PB patterns can be obtained by manipulating printing parameters, such as the concentration of FeCl3 ·K3 Fe(CN)6 , printing speed, and pipette inner diameter. Using a 0.1 M KCl (pH 4) electrolyte, the printed PB pattern is consistently and reversibly converted to Prussian white (CV potential range: -0.2-0.5 V) with 200 CV cycles. The PB-based EC display with a navigation function integrated into a smart contact lens is able to display directions to a destination to a user by receiving GPS coordinates in real time. This facile method for forming PB micro-patterns could be used for advanced EC displays and various functional devices.

In situ synthesis of hierarchically-assembled three-dimensional ZnS nanostructures and 3D printed visualization.

Nanomaterials have gained enormous interest in improving the performance of energy harvest systems, biomedical devices, and high-strength composites. Many studies were performed fabricating more elaborate and heterogeneous nanostructures then the structures were characterized using TEM tomographic images, upgrading the fabrication technique. Despite the effort, intricate fabrication process, agglomeration characteristic, and non-uniform output were still limited to presenting the 3D panoramic views straightforwardly. Here we suggested in situ synthesis method to prepare complex and hierarchically-assembled nanostructures that consisted of ZnS nanowire core and nanoparticles under Ag2S catalyst. We demonstrated that the vaporized Zn and S were solidified in different shapes of nanostructures with the temperatures solely. To our knowledge, this is the first demonstration of synthesizing heterogeneous nanostructures, consisting of a nanowire from the vapor-liquid-solid and then nanoparticles from the vapor-solid grown mechanism by in situ temperature control. The obtained hierarchically-assembled ZnS nanostructures were characterized by various TEM technologies, verifying the crystal growth mechanism. Lastly, electron tomography and 3D printing enabled the nanoscale structures to visualize with centimeter scales. The 3D printing from randomly fabricated nanomaterials is rarely performed to date. The collaborating work could offer a better opportunity to fabricate advanced and sophisticated nanostructures.

3D-printed NiFe-layered double hydroxide pyramid electrodes for enhanced electrocatalytic oxygen evolution reaction.

Electrochemical water splitting has been considered one of the most promising methods of hydrogen production, which does not cause environmental pollution or greenhouse gas emissions. Oxygen evolution reaction (OER) is a significant step for highly efficient water splitting because OER involves the four electron transfer, overcoming the associated energy barrier that demands a potential greater than that required by hydrogen evolution reaction. Therefore, an OER electrocatalyst with large surface area and high conductivity is needed to increase the OER activity. In this work, we demonstrated an effective strategy to produce a highly active three-dimensional (3D)-printed NiFe-layered double hydroxide (LDH) pyramid electrode for OER using a three-step method, which involves direct-ink-writing of a graphene pyramid array and electrodeposition of a copper conducive layer and NiFe-LDH electrocatalyst layer on printed pyramids. The 3D pyramid structures with NiFe-LDH electrocatalyst layers increased the surface area and the active sites of the electrode and improved the OER activity. The overpotential (η) and exchange current density (i0) of the NiFe-LDH pyramid electrode were further improved compared to that of the NiFe-LDH deposited Cu (NiFe-LDH/Cu) foil electrode with the same base area. The 3D-printed NiFe-LDH electrode also exhibited excellent durability without potential decay for 60 h. Our 3D printing strategy provides an effective approach for the fabrication of highly active, stable, and low-cost OER electrocatalyst electrodes.

Three-Dimensional Perovskite Nanopixels for Ultrahigh-Resolution Color Displays and Multilevel Anticounterfeiting.

Hybrid perovskites are emerging as a promising, high-performance luminescent material; however, the technological challenges associated with generating high-resolution, free-form perovskite structures remain unresolved, limiting innovation in optoelectronic devices. Here, we report nanoscale three-dimensional (3D) printing of colored perovskite pixels with programmed dimensions, placements, and emission characteristics. Notably, a meniscus comprising femtoliters of ink is used to guide a highly confined, out-of-plane crystallization process, which generates 3D red, green, and blue (RGB) perovskite nanopixels with ultrahigh integration density. We show that the 3D form of these nanopixels enhances their emission brightness without sacrificing their lateral resolution, thereby enabling the fabrication of high-resolution displays with improved brightness. Furthermore, 3D pixels can store and encode additional information into their vertical heights, providing multilevel security against counterfeiting. The proof-of-concept experiments demonstrate the potential of 3D printing to become a platform for the manufacture of smart, high-performance photonic devices without design restrictions.

Metals by Micro-Scale Additive Manufacturing: Comparison of Microstructure and Mechanical Properties.

Many emerging applications in microscale engineering rely on the fabrication of 3D architectures in inorganic materials. Small-scale additive manufacturing (AM) aspires to provide flexible and facile access to these geometries. Yet, the synthesis of device-grade inorganic materials is still a key challenge toward the implementation of AM in microfabrication. Here, a comprehensive overview of the microstructural and mechanical properties of metals fabricated by most state-of-the-art AM methods that offer a spatial resolution ≤10 µm is presented. Standardized sets of samples are studied by cross-sectional electron microscopy, nanoindentation, and microcompression. It is shown that current microscale AM techniques synthesize metals with a wide range of microstructures and elastic and plastic properties, including materials of dense and crystalline microstructure with excellent mechanical properties that compare well to those of thin-film nanocrystalline materials. The large variation in materials' performance can be related to the individual microstructure, which in turn is coupled to the various physico-chemical principles exploited by the different printing methods. The study provides practical guidelines for users of small-scale additive methods and establishes a baseline for the future optimization of the properties of printed metallic objects-a significant step toward the potential establishment of AM techniques in microfabrication.

3D-Printed Quantum Dot Nanopixels.

The pixel is the minimum unit used to represent or record information in photonic devices. The size of the pixel determines the density of the integrated information, such as the resolution of displays or cameras. Most methods used to produce display pixels are based on two-dimensional patterning of light-emitting materials. However, the brightness of the pixels is limited when they are miniaturized to nanoscale dimensions owing to their limited volume. Herein, we demonstrate the production of three-dimensional (3D) pixels with nanoscale dimensions based on the 3D printing of quantum dots embedded in polymer nanowires. In particular, a femtoliter meniscus was used to guide the solidification of liquid inks to form vertically freestanding nanopillar structures. Based on the 3D layout, we show high-density integration of color pixels, with a lateral dimension of 620 nm and a pitch of 3 µm for each of the red, green, and blue colors. The 3D structure enabled a 2-fold increase in brightness without significant effects on the spatial resolution of the pixels. In addition, we demonstrate individual control of the brightness based on a simple adjustment of the height of the 3D pixels. This method can be used to achieve super-high-resolution display devices and various photonic applications across a range of disciplines.

3D-printed Cu2O photoelectrodes for photoelectrochemical water splitting.

Photoelectrochemical (PEC) water splitting is an alternative to fossil fuel combustion involving the generation of renewable hydrogen without environmental pollution or greenhouse gas emissions. Cuprous oxide (Cu2O) is a promising semiconducting material for the simple reduction of hydrogen from water, in which the conduction band edge is slightly negative compared to the water reduction potential. However, the solar-to-hydrogen conversion efficiency of Cu2O is lower than the theoretical value due to a short carrier-diffusion length under the effective light absorption depth. Thus, increasing light absorption in the electrode-electrolyte interfacial layer of a Cu2O photoelectrode can enhance PEC performance. In this study, a Cu2O 3D photoelectrode comprised of pyramid arrays was fabricated using a two-step method involving direct-ink-writing of graphene structures. This was followed by the electrodeposition of a Cu current-collecting layer and a p-n homojunction Cu2O photocatalyst layer onto the printed structures. The performance for PEC water splitting was enhanced by increasing the total light absorption area (A a) of the photoelectrode via controlling the electrode topography. The 3D photoelectrode (A a = 3.2 cm2) printed on the substrate area of 1.0 cm2 exhibited a photocurrent (I ph) of -3.01 mA at 0.02 V (vs. RHE), which is approximately three times higher than that of a planar photoelectrode with an A a = 1.0 cm2 (I ph = -0.91 mA). Our 3D printing strategy provides a flexible approach for the design and the fabrication of highly efficient PEC photoelectrodes.

3D Nanoprinting of Perovskites.

As competing with the established silicon technology, organic-inorganic metal halide perovskites are continually gaining ground in optoelectronics due to their excellent material properties and low-cost production. The ability to have control over their shape, as well as composition and crystallinity, is indispensable for practical materialization. Many sophisticated nanofabrication methods have been devised to shape perovskites; however, they are still limited to in-plane, low-aspect-ratio, and simple forms. This is in stark contrast with the demands of modern optoelectronics with freeform circuitry and high integration density. Here, a nanoprecision 3D printing is developed for organic-inorganic metal halide perovskites. The method is based on guiding evaporation-induced perovskite crystallization in mid-air using a femtoliter ink meniscus formed on a nanopipette, resulting in freestanding 3D perovskite nanostructures with a preferred crystal orientation. Stretching the ink meniscus with a pulling process enables on-demand control of the nanostructure's diameter and hollowness, leading to an unprecedented tubular-solid transition. With varying the pulling direction, a layer-by-layer stacking of perovskite nanostructures is successfully demonstrated with programmed shapes and positions, a primary step for additive manufacturing. It is expected that the method has the potential to create freeform perovskite nanostructures for customized optoelectronics.

3D printing of highly conductive silver architectures enabled to sinter at low temperatures.

Silver (Ag) nanoparticle-based inks are frequently used in printed electronics to form conductive patterns, but often require high-temperature sintering to achieve the optimum electrical conductivity, hindering their use in substrates with poor heat resistance. Herein, a three-dimensional (3D) printing strategy to produce highly conductive Ag 3D architectures that can be sintered at low temperatures is reported. This strategy is based on the additive deposition of Ag nanoparticles and microflakes via extrusion-based 3D printing with the Ag ink that involves poly(acrylic acid) (PAA)-stabilized Ag nanoparticles, Ag microflakes, and NaCl - a destabilizing agent. The designed Ag inks are stable and suitable for ink-extrusion 3D printing. In chemical sintering, Cl- can detach PAA from the Ag nanoparticle surface, enabling nanoparticle coalescence and sintering. An elevated annealing temperature induces increased NaCl density in the printed patterns and accelerates the surface and grain boundary diffusion of Ag atoms, contributing to enhance chemical sintering. On annealing at ∼110 °C for 30 min, the printed structures exhibited an electrical conductivity of ∼9.72 × 104 S cm-1, which is ∼15.6% of that of bulk Ag. Complicated Ag architectures with diverse shapes were successfully fabricated on polymeric substrates. Several structural electronic applications were demonstrated by hybrid 3D printing combining our extrusion-based 3D printing and conventional fused deposition modeling (FDM).

Electroless Deposition-Assisted 3D Printing of Micro Circuitries for Structural Electronics.

Three-dimensional (3D) printing is a next-generation free-form manufacturing technology for structural electronics. The realization of structural electronic devices necessitates the direct integration of electronic circuits into 3D objects. However, creating highly conductive, high-resolution patterns in 3D remains a major challenge. Here, we report on a metallic 3D printing method that incorporates electroless deposition (ELD) into the direct ink writing method. Our approach consists of two steps: (1) direct ink writing of catalyst microstructures with a functional catalyst ink containing Ag ions and (2) ELD of Cu onto the printed catalyst structures. High-quality, stable Cu 3D printing is achieved through the design of the Ag catalyst ink; hydroxypropyl cellulose is added as both a rheological modifier (printing) and dissolution inhibitor (ELD). As a result, various two-dimensional (2D) and 3D Cu micro circuitries with high conductivity (∼65% of bulk) can be directly integrated onto 3D plastic substrates without the need for high-temperature annealing. A hybrid strategy that combines ELD-assisted 3D printing and conventional fused deposition modeling enables full fabrication of structural electronic devices. This 3D printing strategy can be a low-cost and facile method for obtaining highly conductive metallic 2D and 3D microstructures in structural electronics.

Flexible Strain Sensors Fabricated by Meniscus-Guided Printing of Carbon Nanotube-Polymer Composites.

Printed strain sensors have promising potential as a human-machine interface (HMI) for health-monitoring systems, human-friendly wearable interactive systems, and smart robotics. Herein, flexible strain sensors based on carbon nanotube (CNT)-polymer composites were fabricated by meniscus-guided printing using a CNT ink formulated from multiwall nanotubes (MWNTs) and polyvinylpyrrolidone (PVP); the ink was suitable for micropatterning on nonflat (or curved) substrates and even three-dimensional structures. The printed strain sensors exhibit a reproducible response to applied tensile and compressive strains, having gauge factors of 13.07 under tensile strain and 12.87 under compressive strain; they also exhibit high stability during ∼1500 bending cycles. Applied strains induce a contact rearrangement of the MWNTs and a change in the tunneling distance between them, resulting in a change in the resistance (Δ R/ R0) of the sensor. Printed MWNT-PVP sensors were used in gloves for finger movement detection; these can be applied to human motion detection and remote control of robotic equipment. Our results demonstrate that meniscus-guided printing using CNT inks can produce highly flexible, sensitive, and inexpensive HMI devices.

Meniscus-on-Demand Parallel 3D Nanoprinting.

Exploiting a femtoliter liquid meniscus formed on a nanopipet is a powerful approach to spatially control mass transfer or chemical reaction at the nanoscale. However, the insufficient reliability of techniques for the meniscus formation still restricts its practical use. We report on a noncontact, programmable method to produce a femtoliter liquid meniscus that is utilized for parallel three-dimensional (3D) nanoprinting. The method based on electrohydrodynamic dispensing enables one to create an ink meniscus at a pipet-substrate gap without physical contact and positional feedback. By guiding the meniscus under rapid evaporation of solvent in air, we successfully fabricate freestanding polymer 3D nanostructures. After a quantitative characterization of the experimental conditions, we show that we can use a multibarrel pipet to achieve parallel fabrication process of clustered nanowires with precise placement. We expect this technique to advance productivity in nanoscale 3D printing.

Precise Placement of Microbubble Templates at Single Entity Resolution.

Microbubbles have been used as a soft template to produce hollow structures for diverse applications in chemistry, materials science, and biomedicine. It is a challenge, however, to control their size and position at single-entity level. We report on an on-demand method to produce and place a single microbubble with programmed size and position. The method exploits scanning an electrolyte-filled micropipette to place a hydrogen (H2) bubble, generated by water electrolysis, on the desired position. The bubble growth is self-limited after the bubble size fits to the pipet aperture, yielding well-controlled bubble size. The bubble growth dynamics within the pipet is successfully investigated by a methodology that combines phase-contrast X-ray imaging and electric-current measurement. We show that the microbubbles, accurately controlled in size and position, can be used for the fabrication of various polypyrrole microcontainer arrays. We expect the scanning-pipet strategy could be generalized for manipulating various soft materials at will.

Three-dimensional Printing of Silver Microarchitectures Using Newtonian Nanoparticle Inks.

Although three-dimensional (3D) printing has recently emerged as a technology to potentially bring about the next industrial revolution, the limited selection of usable materials restricts its use to simple prototyping. In particular, metallic 3D printing with submicrometer spatial resolution is essential for the realization of 3D-printed electronics. Herein, a meniscus-guided 3D printing method that exploits a low-viscosity (∼7 mPa·s) silver nanoparticle (AgNP) ink meniscus with Newtonian fluid characteristics (which is compatible with conventional inkjet printers) to fabricate 3D silver microarchitectures is reported. Poly(acrylic acid)-capped AgNP ink that exhibits a continuous ink flow through a confined nozzle without aggregation is designed in this study. Guiding the ink meniscus with controlled direction and speed enables both vertical pulling and layer-by-layer processing, resulting in the creation of 3D microobjects with designed shapes other than those for simple wiring. Various highly conductive (>104 S·cm-1) 3D metallic patterns are demonstrated for applications in electronic devices. This research is expected to widen the range of materials that can be employed in 3D printing technology, with the aim of moving 3D printing beyond prototyping and into real manufacturing platforms for future electronics.

Three-Dimensional Printing of Highly Conductive Carbon Nanotube Microarchitectures with Fluid Ink.

Moving printed electronics to three dimensions essentially requires advanced additive manufacturing techniques yielding multifunctionality materials and high spatial resolution. Here, we report the meniscus-guided 3D printing of highly conductive multiwall carbon nanotube (MWNT) microarchitectures that exploit rapid solidification of a fluid ink meniscus formed by pulling a micronozzle. To achieve high-quality printing with continuous ink flow through a confined nozzle geometry, that is, without agglomeration and nozzle clogging, we design a polyvinylpyrrolidone-wrapped MWNT ink with uniform dispersion and appropriate rheological properties. The developed technique can produce various desired 3D microstructures, with a high MWNT concentration of up to 75 wt % being obtained via post-thermal treatment. Successful demonstrations of electronic components such as sensing transducers, emitters, and radio frequency inductors are also described herein. We expect that the technique presented in this study will facilitate selection of diverse materials in 3D printing and enhance the freedom of integration for advanced conceptual devices.

Electrodeposition-based 3D Printing of Metallic Microarchitectures with Controlled Internal Structures.

3D printing of metallic microarchitectures with controlled internal structures is realized at room temperature in ambient air conditions by the manipulation of metal ion concentration and pulsed electric potentials in the electrolyte meniscus during the meniscus-guided electrodeposition. Precise control of the printing nozzle enables the drawing of complex 3D microarchitectures with well-defined geometries and positions.

Rearrangement of 1D conducting nanomaterials towards highly electrically conducting nanocomposite fibres for electronic textiles.

Nanocarbon-based conducting fibres have been produced using solution- or dry-spinning techniques. Highly conductive polymer-composite fibres containing large amounts of conducting nanomaterials have not been produced without dispersants, however, because of the severe aggregation of conducting materials in high-concentration colloidal solutions. Here we show that highly conductive (electrical conductivity ~1.5 × 10(5) S m(-1)) polymer-composite fibres containing carbon nanotubes and silver nanowires can be fabricated via a conventional solution-spinning process without any other treatment. Spinning dopes were fabricated by a simple mixing of a polyvinyl alcohol solution in dimethylsulfoxide with a paste of long multi-walled carbon nanotubes dispersed in organic solvents, assisted by quadruple hydrogen-bonding networks and an aqueous silver nanowire dispersion. The high electrical conductivity of the fibre was achieved by rearrangement of silver nanowires towards the fibre skin during coagulation because of the selective favourable interaction between the silver nanowires and coagulation solvents. The prepared conducting fibres provide applications in electronic textiles such as a textile interconnector of light emitting diodes, flexible textile heaters, and touch gloves for capacitive touch sensors.

3D printing of reduced graphene oxide nanowires.

3D printing of reduced graphene oxide (rGO) nanowires is realized at room temperature by local growth of GO at the meniscus formed at a micropipette tip followed by reduction of GO by thermal or chemical treatment. 3D rGO nanowires with diverse and complicated forms are successfully printed, demonstrating their ability to grow in any direction and at the selected sites.