3D Printing of Living Responsive Materials and Devices

3D printing has been intensively explored to fabricate customized structures of responsive materials including hydrogels, liquid‐crystal elastomers, shape‐memory polymers, and aqueous droplets. Herein, a new method and material system capable of 3D‐printing hydrogel inks with programed bacterial cells as responsive components into large‐scale (3 cm), high‐resolution (30 μm) living materials, where the cells can communicate and process signals in a programmable manner, are reported. The design of 3D‐printed living materials is guided by quantitative models that account for the responses of programed cells in printed microstructures of hydrogels. Novel living devices are further demonstrated, enabled by 3D printing of programed cells, including logic gates, spatiotemporally responsive patterning, and wearable devices.     

3D Printed Polymer Photodetectors

Extrusion‐based 3D printing, an emerging technology, has been previously used in the comprehensive fabrication of light‐emitting diodes using various functional inks, without cleanrooms or conventional microfabrication techniques. Here, polymer‐based photodetectors exhibiting high performance are fully 3D printed and thoroughly characterized. A semiconducting polymer ink is printed and optimized for the active layer of the photodetector, achieving an external quantum efficiency of 25.3%, which is comparable to that of microfabricated counterparts and yet created solely via a one‐pot custom built 3D‐printing tool housed under ambient conditions. The devices are integrated into image sensing arrays with high sensitivity and wide field of view, by 3D printing interconnected photodetectors directly on flexible substrates and hemispherical surfaces. This approach is further extended to create integrated multifunctional devices consisting of optically coupled photodetectors and light‐emitting diodes, demonstrating for the first time the multifunctional integration of multiple semiconducting device types which are fully 3D printed on a single platform. The 3D‐printed optoelectronic devices are made without conventional microfabrication facilities, allowing for flexibility in the design and manufacturing of next‐generation wearable and 3D‐structured optoelectronics, and validating the potential of 3D printing to achieve high‐performance integrated active electronic materials and devices.     

Extrusion‐Based 3D Printing of Hierarchically Porous Advanced Battery Electrodes

A highly porous 2D nanomaterial, holey graphene oxide (hGO), is synthesized directly from holey graphene powder and employed to create an aqueous 3D printable ink without the use of additives or binders. Stable dispersions of hydrophilic hGO sheets in water (≈100 mg mL^?1) can be readily achieved. The shear‐thinning behavior of the aqueous hGO ink enables extrusion‐based printing of fine filaments into complex 3D architectures, such as stacked mesh structures, on arbitrary substrates. The freestanding 3D printed hGO meshes exhibit trimodal porosity: nanoscale (4–25 nm through‐holes on hGO sheets), microscale (tens of micrometer‐sized pores introduced by lyophilization), and macroscale (<500 µm square pores of the mesh design), which are advantageous for high‐performance energy storage devices that rely on interfacial reactions to promote full active‐site utilization. To elucidate the benefit of (nano)porosity and structurally conscious designs, the additive‐free architectures are demonstrated as the first 3D printed lithium–oxygen (Li–O₂) cathodes and characterized alongside 3D printed GO‐based materials without nanoporosity as well as nanoporous 2D vacuum filtrated films. The results indicate the synergistic effect between 2D nanomaterials, hierarchical porosity, and overall structural design, as well as the promise of a freeform generation of high‐energy‐density battery systems.     

A New 3D Printing Strategy by Harnessing Deformation,Instability, and Fracture of Viscoelastic Inks

Direct ink writing (DIW) has demonstrated great potential as a multimaterial multifunctional fabrication method in areas as diverse as electronics, structural materials, tissue engineering, and soft robotics. During DIW, viscoelastic inks are extruded out of a 3D printer's nozzle as printed fibers, which are deposited into patterns when the nozzle moves. Hence, the resolution of printed fibers is commonly limited by the nozzle's diameter, and the printed pattern is limited by the motion paths. These limits have severely hampered innovations and applications of DIW 3D printing. Here, a new strategy to exceed the limits of DIW 3D printing by harnessing deformation, instability, and fracture of viscoelastic inks is reported. It is shown that a single nozzle can print fibers with resolution much finer than the nozzle diameter by stretching the extruded ink, and print various thickened or curved patterns with straight nozzle motions by accumulating the ink. A quantitative phase diagram is constructed to rationally select parameters for the new strategy. Further, applications including structures with tunable stiffening, 3D structures with gradient and programmable swelling properties, all printed with a single nozzle are demonstrated. The current work demonstrates that the mechanics of inks plays a critical role in developing 3D printing technology.     

Printed Electronics Based on Inorganic Semiconductors: From Processes and Materials to Devices

Following the ever‐expanding technological demands, printed electronics has shown palpable potential to create new and commercially viable technologies that will benefit from its unique characteristics, such as, large‐area and wide range of substrate compatibility, conformability and low‐cost. Through the last few decades, printed/solution‐processed field‐effect transistors (FETs) and circuits have witnessed immense research efforts, technological growth and increased commercial interests. Although printing of functional inks comprising organic semiconductors has already been initiated in early 1990s, gradually the attention, at least partially, has been shifted to various forms of inorganic semiconductors, starting from metal chalcogenides, oxides, carbon nanotubes and very recently to graphene and other 2D semiconductors. In this review, the entire domain of printable inorganic semiconductors is considered. In fact, thanks to the continuous development of materials/functional inks and novel design/printing strategies, the inorganic printed semiconductor‐based circuits today have reached an operation frequency up to several hundreds of kilohertz with only a few nanosecond time delays at the individual FET/inverter levels; in this regard, often circuits based on hybrid material systems have been found to be advantageous. At the end, a comparison of relative successes of various printable inorganic semiconductor materials, the remaining challenges and the available future opportunities are summarized.     

Lignin‐Based Direct Ink Printed Structural Scaffolds

3D printing of lignocellulosic biomass (cellulose, hemicellulose, and lignin) has attracted increasing attention by using this abundant, sustainable, and ecofriendly material. While cellulose can be easily tailored into a highly viscous ink for 3D printing, after solvent evaporation, the final printed structures become highly porous, fragile, and easily fall apart in water due to its hydrophilic nature. Lignin, another crucial component of natural lignocellulose, has not yet been reported for ink printing due to its unfavorable rheological behavior. Herein, a low‐cost direct ink printing strategy is developed to fabricate lignin‐based 3D structures with lignin no further refined and a more compact microstructure as well as different functionalities compared with printed cellulose. By using a soft triblock copolymer as the crosslinking agent, the rheology of lignin‐based inks can be adjusted from soft to rigid, and even enables vertical printing which requires stiff and self‐supporting features. The lignin‐based inks contain less water (≈40 wt%) and exhibit a much denser, stiffer structure, resulting in a wet tensile strength of ≈30 MPa, compared to only ≈0.6 MPa for printed cellulose. In addition, the unique macromolecular structure of lignin also demonstrates significantly improved stability in water and under heat, as well as UV‐blocking performance.     

A Dynamic Graphene Oxide Network Enables Spray Printing of Colloidal Gels for High‐Performance Micro‐Supercapacitors

Properly controlling the rheological properties of nanoparticle inks is crucial to their printability. Here, it is reported that colloidal gels containing a dynamic network of graphene oxide (GO) sheets can display unusual rheological properties after high‐rate shearing. When mixed with polyaniline nanofiber dispersions, the GO network not only facilitates the gelation process but also serves as an effective energy‐transmission network to allow fast structural recovery after the gel is deformed by high‐rate shearing. This extraordinary fast recovery phenomenon has made it possible to use the conventional air‐brush spray technique to print the gel with high‐throughput and high fidelity on nonplanar flexible surfaces. The as‐printed micro‐supercapacitors exhibit an areal capacitance 4–6 times higher than traditionally spray‐printed ones. This work highlights the hidden potential of 2D materials as functional yet highly efficient rheological enhancers to facilitate industrial processing of nanomaterial‐based devices.     

Printable Transparent Conductive Films for Flexible Electronics

Printed electronics are an important enabling technology for the development of low‐cost, large‐area, and flexible optoelectronic devices. Transparent conductive films (TCFs) made from solution‐processable transparent conductive materials, such as metal nanoparticles/nanowires, carbon nanotubes, graphene, and conductive polymers, can simultaneously exhibit high mechanical flexibility, low cost, and better photoelectric properties compared to the commonly used sputtered indium‐tin‐oxide‐based TCFs, and are thus receiving great attention. This Review summarizes recent advances of large‐area flexible TCFs enabled by several roll‐to‐roll‐compatible printed techniques including inkjet printing, screen printing, offset printing, and gravure printing using the emerging transparent conductive materials. The preparation of TCFs including ink formulation, substrate treatment, patterning, and postprocessing, and their potential applications in solar cells, organic light‐emitting diodes, and touch panels are discussed in detail. The rational combination of a variety of printed techniques with emerging transparent conductive materials is believed to extend the opportunities for the development of printed electronics within the realm of flexible electronics and beyond.     

High‐Performance Materials for 3D Printing in Chemical Synthesis Applications

3D printing has emerged as an enabling technology for miniaturization. High‐precision printing techniques such as stereolithography are capable of printing microreactors and lab‐on‐a‐chip devices for efficient parallelization of biological and biochemical reactions under reduced uptake of reactants. In the world of chemistry, however, up until now, miniaturization has played a minor role. The chemical and thermal stability of regular 3D printing resins is insufficient for sustaining the harsh conditions of chemical reactions. Novel material formulations that produce highly stable 3D‐printed chips are highly sought for bringing chemistry up‐to‐date on the development of miniaturization. In this work, a brief review of recent developments in highly stable materials for 3D printing is given. This work focuses on three highly stable 3D‐printable material systems: transparent silicate glasses, ceramics, and fluorinated polymers. It is further demonstrated that 3D printing is also a versatile technique for surface structuring of polymers to enhance their wetting performance. Such micro/nanostructuring is key to selectively wetting surface patterns that are versatile for chemical arrays and droplet synthesis.     

3D Printed Photoresponsive Devices Based on Shape Memory Composites

Compared with traditional stimuli‐responsive devices with simple planar or tubular geometries, 3D printed stimuli‐responsive devices not only intimately meet the requirement of complicated shapes at macrolevel but also satisfy various conformation changes triggered by external stimuli at the microscopic scale. However, their development is limited by the lack of 3D printing functional materials. This paper demonstrates the 3D printing of photoresponsive shape memory devices through combining fused deposition modeling printing technology and photoresponsive shape memory composites based on shape memory polymers and carbon black with high photothermal conversion efficiency. External illumination triggers the shape recovery of 3D printed devices from the temporary shape to the original shape. The effect of materials thickness and light density on the shape memory behavior of 3D printed devices is quantified and calculated. Remarkably, sunlight also triggers the shape memory behavior of these 3D printed devices. This facile printing strategy would provide tremendous opportunities for the design and fabrication of biomimetic smart devices and soft robotics.     

High-resolution electrohydrodynamic jet printing

Efforts to adapt and extend graphic arts printing techniques for demanding device applications in electronics, biotechnology and microelectromechanical systems have grown rapidly in recent years. Here, we describe the use of electrohydrodynamically induced fluid flows through fine microcapillary nozzles for jet printing of patterns and functional devices with submicrometre resolution. Key aspects of the physics of this approach, which has some features in common with related but comparatively low-resolution techniques for graphic arts, are revealed through direct high-speed imaging of the droplet formation processes. Printing of complex patterns of inks, ranging from insulating and conducting polymers, to solution suspensions of silicon nanoparticles and rods, to single-walled carbon nanotubes, using integrated computer-controlled printer systems illustrates some of the capabilities. High-resolution printed metal interconnects, electrodes and probing pads for representative circuit patterns and functional transistors with critical dimensions as small as 1 mum demonstrate potential applications in printed electronics.     

Colloidal Nanosurfactants for 3D Conformal Printing of 2D van der Waals Materials

Printing techniques using nanomaterials have emerged as a versatile tool for fast prototyping and potentially large-scale manufacturing of functional devices. Surfactants play a significant role in many printing processes due to their ability to reduce interfacial tension between ink solvents and nanoparticles and thus improve ink colloidal stability. Here, a colloidal graphene quantum dot (GQD)-based nanosurfactant is reported to stabilize various types of 2D materials in aqueous inks. In particular, a graphene ink with superior colloidal stability is demonstrated by GQD nanosurfactants via the π–π stacking interaction, leading to the printing of multiple high-resolution patterns on various substrates using a single printing pass. It is found that nanosurfactants can significantly improve the mechanical stability of the printed graphene films compared with those of conventional molecular surfactant, as evidenced by 100 taping, 100 scratching, and 1000 bending cycles. Additionally, the printed composite film exhibits improved photoconductance using UV light with 400 nm wavelength, arising from excitation across the nanosurfactant bandgap. Taking advantage of the 3D conformal aerosol jet printing technique, a series of UV sensors of heterogeneous structures are directly printed on 2D flat and 3D spherical substrates, demonstrating the potential of manufacturing geometrically versatile devices based on nanosurfactant inks.     

3D Printing of Customized Li‐Ion Batteries with Thick Electrodes

The growing demand for rechargeable lithium‐ion batteries (LIBs) with higher capacity in customized geometries underscores the need for new battery materials, architectures, and assembly strategies. Here, the design, fabrication, and electrochemical performance of fully 3D printed LIBs composed of thick semisolid electrodes that exhibit high areal capacity are reported. Specifically, semisolid cathode and anode inks, as well as UV curable packaging and separator inks for direct writing of LIBs in arbitrary geometries are created. These fully 3D printed and packaged LIBs, which are encased between two glassy carbon current collectors, deliver an areal capacity of 4.45 mAh cm^?2 at a current density of 0.14 mA cm^?2, which is equivalent to 17.3 Ah L^?1. The ability to produce high‐performance LIBs in customized form factors opens new avenues for integrating batteries directly within 3D printed objects.     

3D Printing of Freestanding MXene Architectures for Current‐Collector‐Free Supercapacitors

Additive manufacturing (AM) technologies appear as a paradigm for scalable manufacture of electrochemical energy storage (EES) devices, where complex 3D architectures are typically required but are hard to achieve using conventional techniques. The combination of these technologies and innovative material formulations that maximize surface area accessibility and ion transport within electrodes while minimizing space are of growing interest. Herein, aqueous inks composed of atomically thin (1–3 nm) 2D Ti₃C₂T_x with large lateral size of about 8 µm possessing ideal viscoelastic properties are formulated for extrusion‐based 3D printing of freestanding, high specific surface area architectures to determine the viability of manufacturing energy storage devices. The 3D‐printed device achieves a high areal capacitance of 2.1 F cm^?2 at 1.7 mA cm^?2 and a gravimetric capacitance of 242.5 F g^?1 at 0.2 A g^?1 with a retention of above 90% capacitance for 10 000 cycles. It also exhibits a high energy density of 0.0244 mWh cm^?2 and a power density of 0.64 mW cm^?2 at 4.3 mA cm^?2. It is anticipated that the sustainable printing and design approach developed in this work can be applied to fabricate high‐performance bespoke multiscale and multidimensional architectures of functional and structural materials for integrated devices in various applications.     

3D Printed Graphene-Based Metamaterials: Guesting Multi-Functionality in One Gain

Advanced functional materials with fascinating properties and extended structural design have greatly broadened their applications. Metamaterials, exhibiting unprecedented physical properties (mechanical, electromagnetic, acoustic, etc.), are considered frontiers of physics, material science, and engineering. With the emerging 3D printing technology, the manufacturing of metamaterials becomes much more convenient. Graphene, due to its superior properties such as large surface area, superior electrical/thermal conductivity, and outstanding mechanical properties, shows promising applications to add multi-functionality into existing metamaterials for various applications. In this review, the aim is to outline the latest developments and applications of 3D printed graphene-based metamaterials. The structure design of different types of metamaterials and the fabrication strategies for 3D printed graphene-based materials are first reviewed. Then the representative explorations of 3D printed graphene-based metamaterials and multi-functionality that can be introduced with such a combination are further discussed. Subsequently, challenges and opportunities are provided, seeking to point out future directions of 3D printed graphene-based metamaterials.     

3D Printing-Assisted Self-Assembly to Bio-Inspired Bouligand Nanostructures

Architected materials with nano/microscale orders can provide superior mechanical properties; however, reproducing such levels of ordering in complex structures has remained challenging. Inspired by Bouligand structures in nature, here, 3D printing of complex geometries with guided long-order radially twisted chiral hierarchy, using cellulose nanocrystals (CNC)-based inks is presented. Detailed rheological measurements, in situ flow analysis, polarized optical microscopy (POM), and director field analysis are employed to evaluate the chiral assembly over the printing process. It is demonstrated that shear flow forces inside the 3D printer's nozzle orient individual CNC particles forming a pseudo-nematic phase that relaxes to uniformly aligned concentric chiral nematic structures after the flow cessation. Acrylamide, a photo-curable monomer, is incorporated to arrest the concentric chiral arrangements within the printed filaments. The time series POM snapshots show that adding the photo-curable monomer at the optimized concentrations does not interfere with chiral self-assemblies and instead increases the chiral relaxation rate. Due to the liquid-like nature of the as-printed inks, optimized Carbopol microgels are used to support printed filaments before photo-polymerization. By paving the path towards developing bio-inspired materials with nanoscale hierarchies in larger-scale printed constructs, this biomimetic approach expands 3D printing materials beyond what has been realized so far.     

Elevated‐Temperature 3D Printing of Hybrid Solid‐State Electrolyte for Li‐Ion Batteries

While 3D printing of rechargeable batteries has received immense interest in advancing the next generation of 3D energy storage devices, challenges with the 3D printing of electrolytes still remain. Additional processing steps such as solvent evaporation were required for earlier studies of electrolyte fabrication, which hindered the simultaneous production of electrode and electrolyte in an all‐3D‐printed battery. Here, a novel method is demonstrated to fabricate hybrid solid‐state electrolytes using an elevated‐temperature direct ink writing technique without any additional processing steps. The hybrid solid‐state electrolyte consists of solid poly(vinylidene fluoride‐hexafluoropropylene) matrices and a Li⁺‐conducting ionic‐liquid electrolyte. The ink is modified by adding nanosized ceramic fillers to achieve the desired rheological properties. The ionic conductivity of the inks is 0.78 × 10 ^?3 S cm^?1. Interestingly, a continuous, thin, and dense layer is discovered to form between the porous electrolyte layer and the electrode, which effectively reduces the interfacial resistance of the solid‐state battery. Compared to the traditional methods of solid‐state battery assembly, the directly printed electrolyte helps to achieve higher capacities and a better rate performance. The direct fabrication of electrolyte from printable inks at an elevated temperature will shed new light on the design of all‐3D‐printed batteries for next‐generation electronic devices.     

MXene Printing and Patterned Coating for Device Applications

As a thriving member of the 2D nanomaterials family, MXenes, i.e., transition metal carbides, nitrides, and carbonitrides, exhibit outstanding electrochemical, electronic, optical, and mechanical properties. They have been exploited in many applications including energy storage, electronics, optoelectronics, biomedicine, sensors, and catalysis. Compared to other 2D materials, MXenes possess a unique set of properties such as high metallic conductivity, excellent dispersion quality, negative surface charge, and hydrophilicity, making them particularly suitable as inks for printing applications. Printing and pre/post-patterned coating methods represent a whole range of simple, economically efficient, versatile, and eco-friendly manufacturing techniques for devices based on MXenes. Moreover, printing can allow for complex 3D architectures and multifunctionality that are highly required in various applications. By means of printing and patterned coating, the performance and application range of MXenes can be dramatically increased through careful patterning in three dimensions; thus, printing/coating is not only a device fabrication tool but also an enabling tool for new applications as well as for industrialization.     

Recent Advances on 3D Printing Technique for Thermal‐Related Applications

Advances in ink formulation and printing techniques make producing material systems with new and versatile characteristics and functionalities possible. Additive manufacturing or 3D printing enables fabricating complex structures at a faster production rate using different types of materials for various applications. Recently, 3D printing methods are being studied for thermal‐related applications. In this paper, the authors review recent progress of materials and printing techniques for thermal application devices using composite materials.

     

3D‐Printed Biomimetic Super‐Hydrophobic Structure for Microdroplet Manipulation and Oil/Water Separation

Biomimetic functional surfaces are attracting increasing attention for various technological applications, especially the superhydrophobic surfaces inspired by plant leaves. However, the replication of the complex hierarchical microstructures is limited by the traditional fabrication techniques. In this paper, superhydrophobic micro‐scale artificial hairs with eggbeater heads inspired by Salvinia molesta leaf was fabricated by the Immersed surface accumulation three dimensional (3D) printing process. Multi‐walled carbon nanotubes were added to the photocurable resins to enhance the surface roughness and mechanical strength of the microstructures. The 3D printed eggbeater surface reveals interesting properties in terms of superhydrophobilicity and petal effect. The results show that a hydrophilic material can macroscopically behave as hydrophobic if a surface has proper microstructured features. The controllable adhesive force (from 23 μN to 55 μN) can be easily tuned with different number of eggbeater arms for potential applications such as micro hand for droplet manipulation. Furthermore, a new energy‐efficient oil/water separation solution based on our biomimetic structures was demonstrated. The results show that the 3D‐printed eggbeater structure could have numerous applications, including water droplet manipulation, 3D cell culture, micro reactor, oil spill clean‐up, and oil/water separation.