3D Printing of Hydrogels for Stretchable Ionotronic Devices

In the booming development of flexible electronics represented by electronic skins, soft robots, and human–machine interfaces, 3D printing of hydrogels, an approach used by the biofabrication community, is drawing attention from researchers working on hydrogel-based stretchable ionotronic devices. Such devices can greatly benefit from the excellent patterning capability of 3D printing in three dimensions, as well as the free design complexity and easy upscale potential. Compared to the advanced stage of 3D bioprinting, 3D printing of hydrogel ionotronic devices is in its infancy due to the difficulty in balancing printability, ionic conductivity, shape fidelity, stretchability, and other functionalities. In this review, a guideline is provided on how to utilize the power of 3D printing in building high-performance hydrogel-based stretchable ionotronic devices mainly from a materials’ point of view, highlighting the systematic approach to balancing the printability, printing quality, and performance of printed devices. Various 3D printing methods for hydrogels are introduced, and then the ink design principles, balancing printing quality, printed functions, such as elastic conductivity, self-healing ability, and device (e.g., flexible sensors, shape-morphing actuators, soft robots, electroluminescent devices, and electrochemical biosensors) performances are discussed. In conclusion, perspectives on the future directions of this exciting field are presented.     

A Review of 3D Printing Technologies for Soft Polymer Materials

Soft polymer materials, which are similar to human tissues, have played critical roles in modern interdisciplinary research. Compared with conventional methods, 3D printing allows rapid prototyping and mass customization and is ideal for processing soft polymer materials. However, 3D printing of soft polymer materials is still in the early stages of development and is facing many challenges including limited printable materials, low printing resolution and speed, and poor functionalities. The present review aims to summarize the ideas to address these challenges. It focuses on three points: 1) how to develop printable materials and make unprintable materials printable, 2) how to choose suitable methods and improve printing resolution, and 3) how to directly construct functional structures/systems with 3D printing. After a brief introduction on this topic, the mainstream 3D printing technologies for printing soft polymer materials are reviewed, with an emphasis on improving printing resolution and speed, choosing suitable printing techniques, developing printable materials, and printing multiple materials. Moreover, the state‐of‐the‐art advancements in multimaterial 3D printing of soft polymer materials are summarized. Furthermore, the revolutions brought about by 3D printing of soft polymer materials for applications similar to biology are highlighted. Finally, viewpoints and future perspectives for this emerging field are discussed.     

3D Printing of Bioinspired Alginate-Albumin Based Instant Gel Ink with Electroconductivity and Its Expansion to Direct Four-Axis Printing of Hollow Porous Tubular Constructs without Supporting Materials

A successful 3D printable hydrogel ink needs not only biofunctionalities but also minimal fabrication steps such as multiple crosslinking sites, high printability, cytocompatibility, high shape fidelity, stability, shear thinning, robust properties, and less time-consuming processing steps, by maximizing known material chemistries and functionalities. This work reports a novel bioinspired conjugate with polysaccharide (alginate)–tannic acid (TA)–protein (bovine serum albumin) to fabricate proteoglycan-like gels, which are 3D printable with multilayers, shear-thinning, elastic, electroconductive (with carbon nanotubes), controlled crosslinking/degradation through multiple crosslinking mechanisms (TA, Ca²⁺ ions, and NaIO₄ oxidation), and interactions with cytocompatible hydrogel system. The synthesis process is simple, and gelation (within 2 h) is ensured without any chemical crosslinking agents (at room temperature). While cell-adhesive albumin largely improves cytocompatibility, carbon nanotubes in the gel give electrical conductivity in the different four-axis 3D printed structures, including large hollow tubular constructs. This work demonstrates promising results of electroconductive proteoglycan-like gel ink to address the challenges in 3D/four-axis ink printing such as synthesis, printability, shape fidelity, electroconductivity, controlled fabrication and degradation, cytocompatibility, and multiple crosslinking abilities to maintain the dimensions of the diversely printed constructs.     

Limpet Tooth-Inspired Painless Microneedles Fabricated by Magnetic Field-Assisted 3D Printing

Microneedle arrays show many advantages in drug delivery applications due to their convenience and reduced risk of infection. Compared to other microscale manufacturing methods, 3D printing easily overcomes challenges in the fabrication of microneedles with complex geometric shapes and multifunctional performance. However, due to material characteristics and limitations on printing capability, there are still bottlenecks to overcome for 3D printed microneedles to achieve the mechanical performance needed for various clinical applications. The hierarchical structures in limpet teeth, which are extraordinarily strong, result from aligned fibers of mineralized tissue and protein-based polymer reinforced frameworks. These structures provide design inspiration for mechanically reinforced biomedical microneedles. Here, a bioinspired microneedle array is fabricated using magnetic field-assisted 3D printing (MF-3DP). Micro-bundles of aligned iron oxide nanoparticles (aIOs) are encapsulated by polymer matrix during the printing process. A bioinspired 3D-printed painless microneedle array is fabricated, and suitability of this microneedle patch for drug delivery during long-term wear is demonstrated. The results reported here provide insights into how the geometrical morphology of microneedles can be optimized for the painless drug delivery in clinical trials.     

A Self-Thickening and Self-Strengthening Strategy for 3D Printing High-Strength and Antiswelling Supramolecular Polymer Hydrogels as Meniscus Substitutes

3D printing of high-strength and antiswelling hydrogel-based load-bearing soft tissue scaffolds with similar geometric shape to natural tissues remains a great challenge owing to insurmountable trade-off between strength and printability. Herein, capitalizing on the concentration-dependent H-bonding-strengthened mechanism of supramolecular poly(N-acryloyl glycinamide) (PNAGA) hydrogel, a self-thickening and self-strengthening strategy, that is, loading the concentrated NAGA monomer into the thermoreversible low-strength PNAGA hydrogel is proposed to directly 3D printing latently H-bonding-reinforced hydrogels. The low-strength PNAGA serves to thicken the concentrated NAGA monomer, affording an appropriate viscosity for thermal-assisted extrusion 3D printing of soft PNAGA hydrogels bearing NAGA monomer and initiator, which are further polymerized to eventually generate high-strength and antiswelling hydrogels, due to the reconstruction of strong H-bonding interactions from postcompensatory PNAGA. Diverse polymer hydrogels can be printed with self-thickened corresponding monomer inks. Further, the self-thickened high-strength PNAGA hydrogel is printed into a meniscus, which is implanted in rabbit's knee as a substitute with in vivo outcome showing an appealing ability to efficiently alleviate the cartilage surface wear. The self-thickening strategy is applicable to directly printing a variety of polymer-hydrogel-based tissue engineering scaffolds without sacrificing mechanical strength, thus circumventing problems of printing high-strength hydrogels and facilitating their application scope.     

3D Printing Personalized,Photocrosslinkable Hydrogel Wound Dressings for the Treatment of Thermal Burns

Considering the variations in burns depending on the circumstances that caused them, the need for personalized medicine and care for burn victims is vital to ensure that optimal treatment is provided. With the level of accuracy and customization that 3D printing brings as a technology, there is potential in its use to fabricate wound dressings that can provide better treatment for burn patients, provided that the material of choice has good printability and can be customized while facilitating wound healing. In this study, the versatility of chitosan methacrylate as said material to be used to fabricate customizable wound dressings via 3D printing is investigated. Synthesized chitosan methacrylate is evaluated to be printable, biodegradable, and biocompatible during wound healing. Various drugs relevant to the treatment of burns are then loaded and different multimaterial wound dressing designs containing different dosages are fabricated via 3D printing. The incorporation of said drugs does not significantly affect the printability of chitosan methacrylate, and the incorporation of antimicrobial agents significantly improves its antimicrobial capabilities. Through in vivo models, these variations in wound dressing designs have good wound healing properties and do not cause any adverse effects in the process.     

3D Printable One-Part Carbon Nanotube-Elastomer Ink for Health Monitoring Applications

3D printing of conductive elastomers is a promising route to personalized health monitoring applications due to its flexibility and biocompatibility. Here, a one-part, highly conductive, flexible, stretchable, 3D printable carbon nanotube (CNT)-silicone composite is developed and thoroughly characterized. The one-part nature of the inks: i) enables printing without prior mixing and cures under ambient conditions; ii) allows direct dispensing at ≈100 µm resolution printability on nonpolar and polar substrates; iii) forms both self-supporting and high-aspect-ratio structures, key aspects in additive biomanufacturing that eliminate the need for sacrificial layers; and iv) lends efficient, reproducible, and highly sensitive responses to various tensile and compressive stimuli. The high electrical and thermal conductivity of the CNT-silicone composite is further extended to facilitate use as a flexible and stretchable heating element, with applications in body temperature regulation, water distillation, and dual temperature sensing and Joule heating. Overall, the facile fabrication of this composite points to excellent synergy with direct ink writing and can be used to prepare patient-specific wearable electronics for motion detection and cardiac and respiratory monitoring devices and toward advanced personal health tracking and bionic skin applications.     

Additive Manufacturing of Batteries

Additive manufacturing, i.e., 3D printing, is being increasingly utilized to fabricate a variety of complex‐shaped electronics and energy devices (e.g., batteries, supercapacitors, and solar cells) due to its excellent process flexibility, good geometry controllability, as well as cost and material waste reduction. In this review, the recent advances in 3D printing of emerging batteries are emphasized and discussed. The recent progress in fabricating 3D‐printed batteries through the major 3D‐printing methods, including lithography‐based 3D printing, template‐assisted electrodeposition‐based 3D printing, inkjet printing, direct ink writing, fused deposition modeling, and aerosol jet printing, are first summarized. Then, the significant achievements made in the development and printing of battery electrodes and electrolytes are highlighted. Finally, major challenges are discussed and potential research frontiers in developing 3D‐printed batteries are proposed. It is expected that with the continuous development of printing techniques and materials, 3D‐printed batteries with long‐term durability, favorable safety as well as high energy and power density will eventually be widely used in many fields.     

Shape-Deformable and Locomotive MXene (Ti3C2Tx)-Encapsulated Magnetic Liquid Metal for 3D-Motion-Adaptive Synapses

Owing to their unique surface chemistry, room-temperature pseudoliquidity, and high electrical conductivity, gallium-based liquid metals (LMs) exhibit multifunctionality. To grant deformable and self-flowing characteristics to LMs, magnetic particles are incorporated for precisely controlling the LM motion and shape deformability. However, LM surface-adhesion and corrosivity hinders the integration of LMs into complex circuits and devices owing to potential alloying with other metals and contamination of their surroundings. In this study, a highly conductive Ti₃C₂T_x (MXene)-encapsulated magnetic LM (MX–MLM) is developed using a feasible fabrication method. The MX–MLM comprises magnetic particles suspended within its core and self-assembled MXene flakes on the surface to maintain the nonwettability and high electrical conductivity of a liquid droplet. The noncorrosivity and increased magnetism of the MX–MLM enable nonstick magnetic-field-induced locomotion and shape deformation on various surfaces including metals, oxides, and polymers. Furthermore, the MX–MLM exhibits recyclability and magnetic-field-induced self-healing. To demonstrate its functionality, the MX–MLM is employed as a magnetointeractive, shape-deformable, and locomotive top gate electrode in a transistor fabricated using a ferroelectric polymer gate insulator. The device exhibits excellent magnetointeractive synaptic capability for detecting and learning 3D path information.     

Dynamic Leakage-Free Liquid Metals

Leakage is a significant issue that prevents the widespread application of liquid metals (LMs) and an effective solution has not yet been developed. One potential solution is to use the high surface tension of LMs to encapsulate them in a porous material. However, it is challenging as it is difficult to infuse LMs into tiny pores. This study proposes a bottom-up strategy where LMs are doped with NdFeB@Ag particles, which are then magnetized to form a tight porous structure. This structure is robust and resistant to collapse under mechanical deformation. Therefore, LMs can be reliably immobilized within the pores between the particles, and a dynamic leakage-free state is achieved. The encapsulated LMs demonstrate excellent properties including a large latent heat of 153.46 J cm⁻³, high thermal conductivity of 35.62 W m⁻¹ K⁻¹, and enhanced electrical conductivity of 69.61%, which efficiently extends their functional scope and potential value.     

Direct Ink Writing of Adjustable Electrochemical Energy Storage Device with High Gravimetric Energy Densities

3D printing graphene aerogel with periodic microlattices has great prospects for various practical applications due to their low density, large surface area, high porosity, excellent electrical conductivity, good elasticity, and designed lattice structures. However, the low specific capacitance limits their development in energy storage fields due to the stacking of graphene. Therefore, constructing a graphene‐based 2D materials hybridization aerogel that consists of the pseduocapacitive substance and graphene material is necessary for enhancing electrochemical performance. Herein, 3D printing periodic graphene‐based composite hybrid aerogel microlattices (HAMs) are reported via 3D printing direct ink writing technology. The rich porous structure, high electrical conductivity, and highly interconnected networks of the HAMs aid electron and ion transport, further enabling excellent capacitive performance for supercapacitors. An asymmetric supercapacitor device is assembled by two different 4‐mm‐thick electrodes, which can yield high gravimetric specific capacitance (C_g) of 149.71 F g^?1 at a current density of 0.5 A g^?1 and gravimetric energy density (E_g) of 52.64 Wh kg^?1, and retains a capacitance retention of 95.5% after 10 000 cycles. This work provides a general strategy for designing the graphene‐based mixed‐dimensional hybrid architectures, which can be utilized in energy storage fields.     

4D Printing at the Microscale

3D printing of adaptive and dynamic structures, also known as 4D printing, is one of the key challenges in contemporary materials science. The additional dimension refers to the ability of 3D printed structures to change their properties—for example, shape—over time in a controlled fashion as the result of external stimulation. Within the last years, significant efforts have been undertaken in the development of new responsive materials for printing at the macroscale. However, 4D printing at the microscale is still in its early stages. Thus, this progress report will focus on emerging materials for 4D printing at the microscale as well as their challenges and potential applications. Hydrogels and liquid crystalline and composite materials have been identified as the main classes of materials representing the state of the art of the growing field. For each type of material, the challenges and critical barriers in the material design and their performance in 4D microprinting are discussed. Importantly, further necessary strategies are proposed to overcome the limitations of the current approaches and move toward their application in fields such as biomedicine, microrobotics, or optics.     

Ultraprecise 3D Printed Graphene Aerogel Microlattices on Tape for Micro Sensors and E-Skin

3D printed graphene aerogels hold promise for flexible sensing fields due to their flexibility, low density, conductivity, and piezo-resistivity. However, low printing accuracy/fidelity and stochastic porous networks have hindered both sensing performance and device miniaturization. Here, printable graphene oxide (GO) inks are formulated through modulating oxygen functional groups, which allows printing of self-standing 3D graphene oxide aerogel microlattice (GOAL) with an ultra-high printing resolution of 70 µm. The reduced GOAL (RGOAL) is then stuck onto the adhesive tape as a facile and large-scale strategy to adapt their functionalities into target applications. Benefiting from the printing resolution of 70 µm, RGOAL tape shows better performance and data readability when used as micro sensors and robot e-skin. By adjusting the molecular structure of GO, the research realizes regulation of rheological properties of GO hydrogel and the 3D printing of lightweight and ultra-precision RGOAL, improves the sensing accuracy of graphene aerogel electronic devices and realizes the device miniaturization, expanding the application of graphene aerogel devices to a broader field such as micro robots, which is beyond the reach of previous reports.     

3D Printing of Functional Magnetic Materials: From Design to Applications

The research of functional magnetic materials has become a hot topic in the past few years due to their fast, long-range, and precise response in diverse environments. Functional magnetic devices using different magnetic materials and structure designs have been developed and demonstrated good advantages to enable various applications. However, the required magnetic materials and structure designs for diverse functions also increase the fabrication difficulties while developing such devices. 3D printing technology presents a powerful and promising manufacturing approach to rapidly fabricate functional magnetic devices of complex geometries in multiple materials and scales. Here, various 3D printing strategies and the underlying mechanisms of functional magnetic materials for several primary applications are systematically reviewed, including, magnetic anisotropy for property enhancement, magnetic robots, magnetic components in electronics, and magneto-thermal devices. Finally, the current challenges and future perspectives in engineering 3D printed functional magnetic devices are discussed.     

Wire Sizing and Spacing for Lithographic Printability and Timing Optimization

As the VLSI feature size has already decreased below lithographic wavelength, the printability problem, due to strong diffraction effects, poses a serious threat to the progress of VLSI technology. A circuit layout with poor printability implies that it is difficult to make the printed features on wafers follow designed shapes without distortions. The development of resolution enhancement techniques (RET) can alleviate the printability problem but cannot reverse the trend of deterioration. Moreover, over-usage of RET may dramatically increase photo-mask cost and increase the cycle time for volume production. Thus, there is a strong demand to consider the subwavelength printability problem in circuit layout designs. However, layout printability optimization should not degrade circuit timing performance. In this paper, we introduce a wire sizing and spacing method to improve wire printability with minimal adverse impact on interconnect timing performance. A new printability model is proposed to handle partially coherent illuminations. The complex printability and timing optimization problem is solved in a two-phase approach. The difficulty of the printability optimization due to its multimodal nature is handled with a sensitivity-based heuristic. A coupling aware timing driven continuous wire sizing algorithm is also provided. Lithographic simulation results show that our approach can improve the printability in term of edge placement error (EPE) by 20%-40% without violating timing, wire width, and spacing constraints.     

Direct 3D Printing of Ultralight Graphene Oxide Aerogel Microlattices

Graphene aerogel microlattices (GAMs) hold great prospects for many multifunctional applications due to their low density, high porosity, designed lattice structures, good elasticity, and tunable electrical conductivity. Previous 3D printing approaches to fabricate GAMs require either high content of additives or complex processes, limiting their wide applications. Here, a facile ion‐induced gelation method is demonstrated to directly print GAMs from graphene oxide (GO) based ink. With trace addition of Ca²⁺ ions as gelators, aqueous GO sol converts to printable gel ink. Self‐standing 3D structures with programmable microlattices are directly printed just in air at room temperature. The rich hierarchical pores and high electrical conductivity of GAMs bring admirable capacitive performance for supercapacitors. The gravimetric capacitance (C_s) of GAMs is 213 F g^?1 at 0.5 A g^?1 and 183 F g^?1 at 100 A g^?1, and retains over 90% after 50 000 cycles. The facile, direct 3D printing of neat graphene oxide can promote wide applications of GAMs from energy storage to tissue engineering scaffolds.     

激光辅助三维金属微打印（特邀）

当前微纳尺度的三维金属结构,由于其独特的物化性能和空间构型优势,在科学与工程领域的应用需求日益增多。由此应运而生的各种三维金属微尺度打印技术近年来相继被开发,并引起了广泛关注。在众多技术中,基于激光的三维微打印技术有着非接触加工、制造灵活性好等优势。文中综述了当前一些代表性的激光辅助三维金属微打印技术,总结了各种三维金属微打印的基本原理、技术优势及典型应用。针对高表面光滑度、高熔点、高电导率的三维金属微打印存在的挑战,介绍了超快激光制备玻璃微通道模具法辅助实现三维金属微制造的新技术。最后就三维金属微打印的未来方向和应用前景进行了探讨。     

All‐Printed Flexible and Stretchable Electronics with Pressing or Freezing Activatable Liquid‐Metal–Silicone Inks

Liquid‐metal (LM)‐based flexible and stretchable electronics have attracted widespread interest in wearable computing, human–machine interaction, and soft robotics. However, many current examples are one‐off prototypes, whereas future implementation requires mass production. To address this critical challenge, an integrated multimaterial 3D printing process composed of direct ink writing (DIW) of sealing silicone elastomer and special LM‐silicone (LMS) inks for manufacturing high‐performance LM‐based flexible and stretchable electronics is presented. The LMS ink is a concentrated mixture of LM microdroplets and silicone elastomer and exhibits excellent printability for DIW printing. Guided by a verified theoretical model, a printing process with high resolution and high speed can be easily implemented. Although LMS is not initially conductive, it can be activated by pressing or freezing. Activated LMS possesses good conductivity and significant electrical response to strain. Owing to LMS's unique structure, LMS‐embedded flexible electronics exhibit great damage mitigation, in that no leaking occurs even when damaged. To demonstrate the flexibility of this process in fabricating LM‐based flexible electronics, multilayer soft circuits, strain sensors, and data gloves are printed and investigated. Notably, utilizing LMS's unique activating property, some functional circuits such as one‐time pressing/freezing‐on switch can be printed without any structural design.     

Tough Transient Ionic Junctions Printed with Ionic Microgels

Emerging soft ionotronics better match the human body mechanically and electrically compared to conventional rigid electronics. They hold great potential for human-machine interfaces, wearable and implantable devices, and soft machines. Among various ionotronic devices, ionic junctions play critical roles in rectifying currents as electrical p–n junctions. Existing ionic junctions, however, are limited in electrical and mechanical performance, and are difficult to fabricate and degrade. Herein, the design, fabrication, and characterization of tough transient ionic junctions fabricated via 3D ionic microgel printing is reported. The 3D printing method demonstrates excellent printability and allows one to fabricate ionic junctions of various configurations with high fidelity. By combining ionic microgels, degradable networks, and highly charged biopolymers, the ionic junctions feature high stretchability (stretch limit 27), high fracture energy (>1000 Jm⁻²), excellent electrical performance (current rectification ratio >100), and transient stability (degrade in 1 week). A variety of ionotronic devices, including ionic diodes, ionic bipolar junction transistors, ionic full-wave rectifiers, and ionic touchpads are further demonstrated. This study merges ionotronics, 3D printing, and degradable hydrogels, and will motivate the future development of high-performance transient ionotronics.     

Direct 3D Printed Biomimetic Scaffolds Based on Hydrogel Microparticles for Cell Spheroid Growth

Biocompatible hydrogel inks with shear‐thinning, appropriate yield strength, and fast self‐healing are desired for 3D bioprinting. However, the lack of ideal 3D bioprinting inks with outstanding printability and high structural fidelity, as well as cell‐compatibility, has hindered the progress of extrusion‐based 3D bioprinting for tissue engineering. In this study, novel self‐healable pre‐cross‐linked hydrogel microparticles (pcHμPs) of chitosan methacrylate (CHMA) and polyvinyl alcohol (PVA) hybrid hydrogels are developed and used as bioinks for extrusion‐based 3D printing of scaffolds with high fidelity and biocompatibility. The pcHμPs display excellent shear thinning when injected through a syringe and subsequently self‐heal into gels as shear forces are removed. Numerical simulations indicate that the pcHμPs experience a plug flow in the nozzle with minimal disturbance, which favors a steady and continuous printing. Moreover, the pcHμPs show a self‐supportive yield strength (540 Pa), which is critical for the fidelity of printed constructs. A series of biomimetic constructs with very high aspect ratio and delicate fine structures are directly printed by using the pcHμP ink. The 3D printed scaffolds support the growth of bone‐marrow‐derived mesenchymal stem cells and formation of cell spheroids, which are most important for tissue engineering.