Hydrogel‐Enabled Transfer‐Printing of Conducting Polymer Films for Soft Organic Bioelectronics

The use of conducting polymers such as poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) for the development of soft organic bioelectronic devices, such as organic electrochemical transistors (OECTs), is rapidly increasing. However, directly manipulating conducting polymer thin films on soft substrates remains challenging, which hinders the development of conformable organic bioelectronic devices. A facile transfer‐printing of conducting polymer thin films from conventional rigid substrates to flexible substrates offers an alternative solution. In this work, it is reported that PEDOT:PSS thin films on glass substrates, once mixed with surfactants, can be delaminated with hydrogels and thereafter be transferred to soft substrates without any further treatments. The proposed method allows easy, fast, and reliable transferring of patterned PEDOT:PSS thin films from glass substrates onto various soft substrates, facilitating their application in soft organic bioelectronics. By taking advantage of this method, skin‐attachable tattoo‐OECTs are demonstrated, relevant for conformable, imperceptible, and wearable organic biosensing.     

On the Principles of Printing Sub‐micrometer 3D Structures from Dielectric‐Liquid‐Based Colloids

Dielectrophoresis‐assisted (DEP) on‐demand printing of dielectric‐liquid‐based colloidal gold under room conditions is demonstrated and employed to print 2D and 3D structures with sub‐micrometer feature sizes. The focus of the work is primarily on explaining the physics of the printing process, based on the formation of a controlled sequence of sub‐micrometer drops. The physics of 3D structure formation on the substrate is explained through the visualization and analysis of various time‐scales relevant to the printing process and the pinning of the contact line of the printed colloids. A parametric variation of the related variables, namely the applied voltage and the pulse length, is used to investigate the morphology and topography of a host of basic, printable 2D and 3D features. It is established that it is possible to obtain uniform particle deposits in 2D by filling up an initial coffee‐ring‐type non‐uniform deposit with a series of subsequently formed drops, all obtained during a single electric pulse. Finally, on‐demand production of multilayered, sub‐micrometer gold tracks is demonstrated, where the annealed tracks exhibit exceptionally low electrical resistivity for their sizes, only two times higher than that of bulk gold.     

Three‐dimensional Printing for Catalytic Applications: Current Status and Perspectives

Three‐dimensional (3D) printing, also known as additive manufacturing, is a fabrication method that has recently received worldwide attention. It provides a convenient and economical way to prepare 3D structures in designable ways. As the technology has developed and the operational costs have decreased, the applications of 3D printing have greatly expanded. Catalyst fabrication is a promising area for 3D printing. Printing processes result in better control of catalyst structures and catalyst distribution. In this perspective, a general overview of the commonly available 3D printing methods that are feasible for the preparation of heterogeneous catalysts is given. Additionally, recent works on printing strategies and new materials for catalysts are discussed. Future development is also addressed.     

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.     

Roll‐to‐roll gravure printing of organic photovoltaic modules—insulation of processing defects by an interfacial layer

Gravure printing as direct patterning roll‐to‐roll (R2R) production technology can revolutionize the design of thin‐film organic photovoltaic (OPV) devices by allowing feasible manufacturing of arbitrary‐shaped modules. This makes a distinction to coating methods, such as slot die coating, in which the pattern is limited to continuous stripes. Here, we analyze the thin‐film formation and its influence on OPV module performance as the gravure printing of hole transport and photoactive layers are transferred from laboratory to R2R pilot production environment. Insertion of a 0.8‐nm layer of lithium fluoride (LiF) as an interfacial layer between the active layer and the electron contact provided insulation against the detrimental pinholes formed in the R2R printing process. Using this device configuration, we produced well‐performing R2R‐printed monolithic modules with a mean efficiency of 1.7%. In comparison, reference modules with an efficiency of 2.2% were fabricated using laboratory‐scale bench top sheet‐level process. Surface energy and tension measurements together with optical microscopy were used to analyze the printability of the materials. The pinhole insulation was investigated in detail by processing R2R‐printed OPV modules with different interfacial layer materials and performing electrical measurements under dark and AM1.5 illumination conditions. Furthermore, we analyzed the LiF distribution using X‐ray photoelectron spectroscopy. The insulating nature of the LiF layer to improve module performance was confirmed by manufacturing lithographically artificial pinholes in device structures. The results show the possibility to loosen the production environment constraints and the feasibility of fabricating well‐performing thin‐film devices by R2R gravure printing. Copyright © 2014 John Wiley & Sons, Ltd.     

Conformal Printing of Graphene for Single‐ and Multilayered Devices onto Arbitrarily Shaped 3D Surfaces

Printing has drawn a lot of attention as a means of low per‐unit cost and high throughput patterning of graphene inks for scaled‐up thin‐form factor device manufacturing. However, traditional printing processes require a flat surface and are incapable of achieving patterning onto 3D objects. Here, a conformal printing method is presented to achieve functional graphene‐based patterns onto arbitrarily shaped surfaces. Using experimental design, a water‐insoluble graphene ink with optimum conductivity is formulated. Then single‐ and multilayered electrically functional structures are printed onto a sacrificial layer using conventional screen printing. The print is then floated on water, allowing the dissolution of the sacrificial layer, while retaining the functional patterns. The single‐ and multilayer patterns can then be directly transferred onto arbitrarily shaped 3D objects without requiring any postdeposition processing. Using this technique, conformal printing of single‐ and multilayer functional devices that include joule heaters, resistive deformation sensors, and proximity sensors on hard, flexible, and soft substrates, such as glass, latex, thermoplastics, textiles, and even candies and marshmallows, is demonstrated. This simple strategy promises to add new device and sensing functionalities to previously inert 3D surfaces.     

Multicolor Printing Using Electric‐Field‐Responsive and Photocurable Photonic Crystals

Efficient and large scale printing of photonic crystal patterns with multicolor, multigrayscale, and fine resolution is highly desired due to its application in smart prints, sensors, and photonic devices. Here, an electric‐field‐assisted multicolor printing is reported based on electrically responsive and photocurable colloidal photonic crystal, which is prepared by supersaturation‐induced self‐assembly of SiO₂ particles in the mixture of propylene carbonate (PC) and trimethylolpropane ethoxylate triacrylate (ETPTA). This colloidal crystal suspension, named as E‐ink, has tunable structural color, controllable grayscale, and instantly fixable characteristics at the same time because the SiO₂/ETPTA‐PC photonic crystal has metastable and reversible assembly as well as polymerizable features. Lithographical printing with photomask and maskless pixel printing techniques are developed respectively to efficiently prepare multicolor and high‐resolution photonic patterns using a single‐component E‐ink.     

Printing Nanostructures with a Propelled Anti‐Pinning Ink Droplet

Striving for cheap and robust manufacturing processes has prompted efforts to adapt and extend methods for printed electronics and biotechnology. A new “direct‐write” printing method for patterning nanometeric species in addressable locations has been developed, by means of evaporative deposition from a propelled anti‐pinning ink droplet (PAPID) in a manner analogous to a snail‐trail. Three velocity‐controlled deposition regimes have been identified; each spontaneously produces distinct and well‐defined self‐assembled deposition patterns. Unlike other technologies that rely on overlapping droplets, PAPIDs produce continuous patterns that can be formed on rigid or flexible substrates, even within 3D concave closed shapes, and have the ability to control the thickness gradient along the pattern. This versatile low cost printing method can produce a wide range of unusual electronic systems not attainable by other methods.     

Ion‐Conductive,Viscosity‐Tunable Hexagonal Boron Nitride Nanosheet Inks

Liquid‐phase exfoliation of layered solids holds promise for the scalable production of 2D nanosheets. When combined with suitable solvents and stabilizing polymers, the rheology of the resulting nanosheet dispersions can be tuned for a variety of additive manufacturing methods. While significant progress is made in the development of electrically conductive nanosheet inks, minimal effort is applied to ion‐conductive nanosheet inks despite their central role in energy storage applications. Here, the formulation of viscosity‐tunable hexagonal boron nitride (hBN) inks compatible with a wide range of printing methods that span the spectrum from low‐viscosity inkjet printing to high‐viscosity blade coating is demonstrated. The inks are prepared by liquid‐phase exfoliation with ethyl cellulose as the polymer dispersant and stabilizer. Thermal annealing of the printed structures volatilizes the polymer, resulting in a porous microstructure and the formation of a nanoscale carbonaceous coating on the hBN nanosheets, which promotes high wettability to battery electrolytes. The final result is a printed hBN nanosheet film that possesses high ionic conductivity, chemical and thermal stability, and electrically insulating character, which are ideal characteristics for printable battery components such as separators. Indeed, lithium‐ion battery cells based on printed hBN separators reveal enhanced electrochemical performance that exceeds commercial polymer separators.     

工艺亭子三维造型与3D打印

3D打印是最近几年开始流行的一种快速成形技术,它以数字模型文件为基础,通过逐层打印的方式来构造物体。被认为推动了第三次工业革命进程的3D打印技术,涉及信息技术、材料科学、精密机械等多个方面。投入民用工业是近年来的事,多用于大型制造业。本文以工艺亭子为载体,介绍3D打印技术,并通过UP打印机完成工艺亭子的3D打印。通过3D打印过程分析得出目前3D打印技术的优势和不足。     

3D Printed High‐Loading Lithium‐Sulfur Battery Toward Wearable Energy Storage

Wearable electronic devices are the new darling of consumer electronics, and energy storage devices are an important part of them. Here, a wearable lithium‐sulfur (Li‐S) bracelet battery using three‐dimensional (3D) printing technology (additive manufacturing) is designed and manufactured for the first time. The bracelet battery can be easily worn to power the wearable device. The “additive” manufacturing characteristic of 3D printing provides excellent controllability of the electrode thickness with much simplified process in a cost‐effective manner. Due to the conductive 3D skeleton providing interpenetrating transmission paths and channels for electrons and ions, the 3D Li‐S battery can provide 505.4 mAh g^?1 specific capacity after 500 cycles with an active material loading as high as 10.2 mg cm^?1. The practicality is illustrated by wearing the bracelet battery on the wrist and illuminating the red light‐emitting diode. Therefore, the bracelet battery manufactured by 3D printing technology can address the needs of the wearable power supply.     

Steady‐State and Transient Behavior of Organic Electrochemical Transistors

In recent years, organic electrochemical transistors (OECTs) have emerged as attractive devices for a variety of applications, particularly in the area of sensing. While the electrical characteristics of OECTs are analogous to those of conventional organic field effect transistors, appropriate models for OECTs have not yet been developed. In particular, little is known about the transient characteristics of OECTs, which are determined by a complex interplay between ionic and electronic motion. In this paper a simple model is presented that reproduces the steady‐state and transient response of OECTs by considering these devices in terms of an ionic and an electronic circuit. A simple analytical expression is derived that can be used to fit steady‐state OECT characteristics. For the transient regime, comparison with experimental data allowed an estimation of the hole mobility in poly(3,4‐ethylenedioxythiophene) doped with poly(styrene sulfonate). This work paves the way for rational optimization of OECTs.     

Electrohydrodynamically Printed High‐Resolution Full‐Color Hybrid Perovskites

Hybrid perovskites show enormous potential for display due to their tunable emission, high color purity, strong photoluminescence and electroluminescence. For display applications, full‐color and high‐resolution patterning is compulsory, however, current perovskite processing such as spin‐coating fails to meet these requirements. Here, electrohydrodynamic (EHD) printing, with the unique advantages of high‐resolution patterning and large scalability, is introduced to fabricate full‐color perovskite patterns. Perovskite inks via simple precursor mixing are prepared to in situ crystallize tunable‐ and bright‐photoluminescence perovskite arrays without adding antisolvent. Through optimizing the EHD printing process, a high‐resolution dot matrix of 5 µm is achieved. The as‐printed patterns and pictures show full color and high controllability in micrometer dimension, indicating that the EHD printing is a competitive technique for future halide perovskite‐based high‐quality display.     

Emission Area Patterning of Organic Light‐Emitting Diodes (OLEDs) via Printed Dielectrics

Solution‐processibility is one of the distinguished traits of organic light‐emitting diodes (OLEDs) compared to existing solid‐state LED technologies. It allows new opportunities which can simplify the fabrication and potentially reduce the cost of manufacturing process. Emission area patterning is one of the crucial fabrication steps and it usually involves subtractive methods, such as photolithography or etching. Here, printing techniques are used to pattern the emission area of blade‐coated OLED layers. The print qualities of a number of printing schemes are characterized and compared. Spray coating and screen printing are used to deposit dielectrics with desired patterns on the OLED layers. At luminance of 1000 cd m⁻² the OLEDs patterned using spray‐coated and screen‐printed dielectric show current density of 8.2 and 10.1 mA cm⁻², external quantum efficiency (EQE) of 2.1% and 2.1%, and luminous efficacy of 5.5 and 6.3 lm W⁻¹, respectively. The OLED characteristics and features of each printing scheme in depositing the dielectric layer are discussed. The printing methods are further applied to demonstrate displays with complex shapes and a seven‐segment display.     

Fully Printed Light‐Emitting Electrochemical Cells Utilizing Biocompatible Materials

The use of biomaterials and bioinspired concepts in electronics will enable the fabrication of transient and disposable technologies within areas ranging from smart packaging and advertisement to healthcare applications. In this work, the use of a nonhalogenated biodegradable solid polymer electrolyte based on poly(ε‐caprolactone‐co‐trimethylene carbonate) and tetrabutylammonium bis‐oxalato borate in light‐emitting electrochemical cells (LECs) is presented. It is shown that the spin‐cast devices exhibit current efficiencies of ≈2 cd A^?1 with luminance over ≈12 000 cd m^?2, an order of magnitude higher than previous bio‐based LECs. By a combination of industrially relevant techniques (i.e., inkjet printing and blade coating), the fabrication of LEC devices on a cellulose‐based flexible biodegradable substrate showing lifetimes compatible with transient applications is demonstrated. The presented results have direct implications toward the industrial manufacturing of biomaterial‐based light‐emitting devices with potential use in future biodegradable/biocompatible electronics.     

Perovskite and Organic Solar Cells Fabricated by Inkjet Printing: Progress and Prospects

Inkjet printing (IJP) technology, adapted from home and office printing, has proven to be an essential research tool and industrial manufacturing technique in a wide range of printed electronic technologies, including optoelectronics. Its primary advantage over other deposition methods is the low‐cost and maskless on‐demand patterning, which offers unmatched freedom‐of‐design. Additional benefits include the efficient use of materials, contactless high‐resolution deposition, and scalability, enabling rapid translation of learning from small‐scale, laboratory‐based research into large‐scale industrial roll‐to‐roll manufacturing. In the development of organic solar cells (OSCs), IJP has enabled the printing of many of the multiple functional layers which comprise the complete cell as part of an additive printing scheme. Although IJP is only recently employed in perovskite solar cell (PeSC) fabrication, it is already showing great promise and is anticipated to find broader application with this class of materials. As OSCs and PeSCs share many common functional materials and device architectures, this review presents a progress report on the IJP of OSCs and PeSCs in order to facilitate knowledge transfer between the two technologies, with critical analyses of the challenges and opportunities also presented.     

Printed Microfluidics

Microfluidics has become an important tool that is useful for a wide range of applications. A drawback for microfluidics is that many of the techniques that are commonly used to fabricate devices are not widely accessible, not scalable to high‐volume manufacturing processes, or both. Recently, a number of printing strategies that were originally developed for other applications have been applied to microfluidic device fabrication. These techniques, which include inkjet printing (IJP), screen printing (SP), and solid wax printing (SWP), are proposed to have a transformative effect on the field. Here microfluidics and printing, are introduced and a list of favorite examples is provided that highlights the accessibility and scalability that the combination is bringing to the field.     

Complex 3D‐Printed Microchannels within Cell‐Degradable Hydrogels

3D‐printing is emerging as a technology to introduce microchannels into hydrogels, for the perfusion of engineered constructs. Although numerous techniques have been developed, new techniques are still needed to obtain the complex geometries of blood vessels and with materials that permit desired cellular responses. Here, a printing process where a shear‐thinning and self‐healing hydrogel “ink” is injected directly into a “support” hydrogel with similar properties is reported. The support hydrogel is further engineered to undergo stabilization through a thiol‐ene reaction, permitting (i) the washing of the ink to produce microchannels and (ii) tunable properties depending on the crosslinker design. When adhesive peptides are included in the support hydrogel, endothelial cells form confluent monolayers within the channels, across a range of printed configurations (e.g., straight, stenosis, spiral). When protease‐degradable crosslinkers are used for the support hydrogel and gradients of angiogenic factors are introduced, endothelial cells sprout into the support hydrogel in the direction of the gradient. This printing approach is used to investigate the influence of channel curvature on angiogenic sprouting and increased sprouting is observed at curved locations. Ultimately, this technique can be used for a range of biomedical applications, from engineering vascularized tissue constructs to modeling in vitro cultures.     

3D Micro‐Extrusion of Graphene‐based Active Electrodes: Towards High‐Rate AC Line Filtering Performance Electrochemical Capacitors

A facile one‐step printing process by 3D micro‐extrusion affording binder‐free thermally reduced graphene oxide (TRGO) based electrochemical capacitors (ECs) that display high‐rate performance is presented. Key intermediates are binder‐free TRGO dispersion printing inks with concentrations up to 15 g L^?1. This versatile printing technique enables easy fabrication of EC electrodes, useful in both aqueous and non‐aqueous electrolyte systems. The as‐prepared TRGO material with high specific surface area (SSA) of 593 m² g^?1 and good electrical conductivity of ≈16 S cm^?1 exhibits impressive charge storage performances. At 100 and 120 Hz, ECs fabricated with TRGO show time constants of 2.5 ms and 2.3 ms respectively. Very high capacitance values are derived at both frequencies ranging from 3.55 mF cm^?2 to 1.76 mF cm^?2. Additionally, these TRGO electrodes can be charged and discharged at very high voltage scan rates up to 15 V s^?1 yielding 4 F cm^?3 with 50% capacitance retention. Electrochemical performance of TRGO electrodes in electrolyte containing tetraethyl ammonium tetrafluoroborate and acetonitrile (TEABF4‐ACN) yields high energy density of 4.43 mWh cm^?3 and power density up to 42.74 kW cm^?3, which is very promising for AC line filtering application and could potentially substitute state of the art electrolytic capacitor technology.     

A Review of Low‐Temperature Solution‐Processed Metal Oxide Thin‐Film Transistors for Flexible Electronics

Solution processing, including printing technology, is a promising technique for oxide thin‐film transistor (TFTs) fabrication because it tends to be a cost‐effective process with high composition controllability and high throughput. However, solution‐processed oxide TFTs are limited by low‐performance and stability issues, which require high‐temperature annealing. This high thermal budget in the fabrication process inhibits oxide TFTs from being applied to flexible electronics. There have been numerous attempts to promote the desired electrical characteristics of solution‐processed oxide TFTs at lower fabrication temperatures. Recent techniques for achieving low‐temperature (<350 °C) solution‐processed and printed oxide TFTs, in terms of the materials, processes, and structural engineering methods currently in use are reviewed. Moreover, the core techniques for both n‐type and p‐type oxide‐based channel layers, gate dielectric layers, and electrode layers in oxide TFTs are addressed. Finally, various multifunctional and emerging applications based on low‐temperature solution‐processed oxide TFTs are introduced and future outlooks for this highly promising research are suggested.