导电油墨及其印刷技术的研究进展

目的 综述导电油墨及其印刷方式的研究进展,为开发价格低廉、性能稳定、导电性优良的导电油墨提供参考。方法 通过查阅文献归纳各类导电油墨的制备方式、印刷方式和应用领域,对导电油墨进行系统分类,比较各类导电油墨的性能和优缺点,并对其印刷技术进行分析,展望了导电油墨的发展前景。结果 目前关于导电油墨的研究集中在纳米银、纳米铜、石墨烯等导电填料的低温烧结油墨,主要采用丝网印刷、喷墨印刷等印刷方式,多用于制备传感器、柔性可穿戴设备等。未来的研究仍需关注如何低成本、低能耗、简单大量地制造导电油墨。结论 导电油墨的制备将与环境友好型的印刷方式相结合,向高导电性、高印刷适性发展,成为印刷电子领域的关键技术。     

液态金属基油墨的印刷适性调控与可拉伸电子应用

目的 调整液态金属基油墨的印刷适性，用于可拉伸电极的印刷法构建。方法 通过超声破碎法减小液态金属微粒直径，降低其表面张力;探究聚氨酯种类和含量对液态金属微粒的分散性、油墨流变性、电极的印刷适性和可拉伸性的影响。结果 引入PU1185制备的液态金属油墨，丝印电极分辨率达58 µm;印制电极展现了良好的导电性和可拉伸性，预拉伸稳定后的电极在100%的应变下拉伸1 000次，电阻变化不超2倍。结论 液态金属基油墨能够用于高分辨电路的加工，在可拉伸电子领域具有可预见的应用前景。     

Low-Temperature Plasma Sintering of Inkjet-Printed Metal Salt Decomposition Inks on Flexible Substrates

Due to their complex formulation, conductive nanoparticle inks for inkjet printing are limited in terms of the types of metals and substrates that can be utilized. A new and simplified class of inks called metal salt decomposition (MSD) inks has the potential to introduce a multitude of metals, which can be printed directly onto a wide range of substrates. Here, the use of atmospheric oxygen plasma to develop polycrystalline Au and Pt films at processing temperatures near room temperature (≈33 °C) with excellent conductivities up to 10⁵ S m⁻¹ is demonstrated. The conformal nature of the ink allows metal films to be printed onto a broad range of temperature-sensitive substrates including polymers, papers, and fabric. The Au ink is then used to build a simple light-emitting diode circuit showing its flexibility, durability, and long-term stability as deposited thin metal films. Additionally, such inks cost less than one-third the price of similar nanoparticle inks highlighting their overall affordability and good stability.     

Surface‐Embedded Stretchable Electrodes by Direct Printing and their Uses to Fabricate Ultrathin Vibration Sensors and Circuits for 3D Structures

Printing is one of the easy and quick ways to make a stretchable wearable electronics. Conventional printing methods deposit conductive materials “on” or “inside” a rubber substrate. The conductors made by such printing methods cannot be used as device electrodes because of the large surface topology, poor stretchability, or weak adhesion between the substrate and the conducting material. Here, a method is presented by which conductive materials are printed in the way of being surface‐embedded in the rubber substrate; hence, the conductors can be widely used as device electrodes and circuits. The printing process involves a direct printing of a metal precursor solution in a block‐copolymer rubber substrate and chemical reduction of the precursor into metal nanoparticles. The electrical conductivity and sensitivity to the mechanical deformation can be controlled by adjusting the number of printing operations. The fabrication of highly sensitive vibration sensors is thus presented, which can detect weak pulses and sound waves. In addition, this work takes advantage of the viscoelasticity of the composite conductor to fabricate highly conductive stretchable circuits for complicated 3D structures. The printed electrodes are also used to fabricate a stretchable electrochemiluminescence display.     

Silver content effect on rheological and electrical properties of silver pastes

The novelty of this work is laboratory formulation of environmentally friendly, water-based silver inks adapted for screen printing. The challenge was also to elaborate inks that can withstand temperatures as high as 900 °C. Indeed, when printed on ceramic substrate, they were sintered at these high temperatures. These inks can replace conductive silver pastes present in the market, today, and containing irritant solvents such as terpineol and other aromatic solvents. Besides, screen printing is considered as an additive technique, thus allowing reducing wastes. Furthermore, only with 72.5% silver, considered as low content compared to commercial inks (≥75%), prepared inks presented good electrical resistivity, 23 nΩ m, close to that of bulk silver resistivity, 16 nΩ m. Formulation of silver inks with spherical particles, 2–3 μm mean diameter, was performed. The aim of the study was to determine silver content effect on pastes rheological behaviour, lines properties (width, thickness and roughness) and electrical properties. Therefore, rheological behaviour of inks was studied; in particular, Casson and Bingham models were applied in order to determine the yield stress. Viscosity evolution as a function of shear rate was also determined. Besides, the thixotropic behaviour of inks was highlighted. Inks were then screen printed on alumina sintered substrates and cured at different temperatures during 15 min. Topography measurements were performed. Line resistivity as small as 35 nΩ m was measured on cured lines. These inks, printed on ceramic tapes, can be used to print microwave transmission lines, for which resistivities lower than 1 mΩ m are requested.     

纳米银导电油墨及其在柔性印刷电子中的应用

目的 探究纳米银导电油墨及其在柔性印刷电子中的应用。方法 通过总结国内外文献,从纳米银颗粒及其导电油墨的制备、印刷工艺、烧结工艺以及在柔性印刷电子技术中的应用几方面总结近年来的研究进展。结果 在油墨制备及使用中,简化制备工艺、降低生产成本、实现绿色环保、低温烧结,同时提高油墨的基材适应性是未来纳米银导电油墨的改进重点。直写技术具有精度高、速度快等优势,正逐渐替代丝网印刷技术成为主流。烧结工艺的研究重点在于实现低温烧结,其中化学烧结工艺简单,但提高导电性是研究重点。其他烧结方式则设备昂贵,环境要求高。结论 作为功能性电子材料,纳米银导电油墨因出色的电性能和印刷适性,正在被广泛应用于柔性印刷电子中。近年来通过对纳米银及其导电油墨的深入研究及技术改进,在纳米银颗粒的制备、低温烧结技术、节能环保加工工艺等方面获得了一定的进展。与此同时,将其作为功能材料应用于制备柔性传感器中,RFID标签天线、柔性电极、超级电容器、太阳能电池等正受到广泛研究与应用。     

Fabrication of extremely conductive high-aspect silver traces buried in hot-embossed polycarbonate films via the direct gravure doctoring method

Depositing inks on a planar substrate by printing is a facile way to fabricate conductive traces and other complicated functional devices. However, irrespective of the printing methods used, the thickness of the inks has an upper limit due to their fluidic property and subsequent wetting on the substrates. Herein, we present a method for creating high-aspect ratio conductive traces by combining hot-embossing and gravure doctoring techniques. Binary-sized colloidal pastes containing Ag nanoparticles and micrometer-sized spherical Ag powder additives were filled using a doctor blade in the grooves of polycarbonate (PC) films inscribed via hot-embossing to create buried traces. Under optimal mixing conditions in which the minimum resistivity was achieved, voids between the microparticles provided a pathway for the volatile solvents to smoothly escape from the filled ink and minimized thickness reduction during the thermal sintering process. A fabricated trace buried in the PC film with an aspect ratio of around 3:1 and a linewidth of 55 μm showed extremely low resistance of less than 10 Ω/m. A flexible transparent heater was developed using the reported binary colloidal paste.     

Polymer‐Assisted Metal Deposition (PAMD) for Flexible and Wearable Electronics: Principle,Materials, Printing,and Devices

The rapid development of flexible and wearable electronics favors low‐cost, solution‐processing, and high‐throughput techniques for fabricating metal contacts, interconnects, and electrodes on flexible substrates of different natures. Conventional top‐down printing strategies with metal‐nanoparticle‐formulated inks based on the thermal sintering mechanism often suffer from overheating, rough film surface, low adhesion, and poor metal quality, which are not desirable for most flexible electronic applications. In recent years, a bottom‐up strategy termed as polymer‐assisted metal deposition (PAMD) shows great promise in addressing the abovementioned challenges. Here, a detailed review of the development of PAMD in the past decade is provided, covering the fundamental chemical mechanism, the preparation of various soft and conductive metallic materials, the compatibility to different printing technologies, and the applications for a wide variety of flexible and wearable electronic devices. Finally, the attributes of PAMD in comparison with conventional nanoparticle strategies are summarized and future technological and application potentials are elaborated.     

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.     

Turning Trash into Treasure: Additive Free MXene Sediment Inks for Screen-Printed Micro-Supercapacitors

Printed functional conductive inks have triggered scalable production of smart electronics such as energy-storage devices, antennas, wearable electronics, etc. Of particular interest are highly conductive-additive-free inks devoid of costly postdeposition treatments to eliminate sacrificial components. Due to the high filler concentration required, formulation of such waste-free inks has proven quite challenging. Here, additive-free, 2D titanium carbide MXene aqueous inks with appropriate rheological properties for scalable screen printing are demonstrated. Importantly, the inks consist essentially of the sediments of unetched precursor and multilayered MXene, which are usually discarded after delamination. Screen-printed structures are presented on paper with high resolution and spatial uniformity, including micro-supercapacitors, conductive tracks, integrated circuit paths, and others. It is revealed that the delaminated nanosheets among the layered particles function as efficient conductive binders, maintaining the mechanical integrity and thus the metallic conductive network. The areal capacitance (158 mF cm⁻²) and energy density (1.64 µWh cm⁻²) of the printed micro-supercapacitors are much superior to other devices based on MXene or graphene. The ink formulation strategy of “turning trash into treasure” for screen printing highlights the potential of waste-free MXene sediment printing for scalable and sustainable production of next-generation wearable smart electronics.     

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.     

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.     

Printed UHF RFID antennas with high efficiencies using nano-particle silver ink

One of the most popular targets of conductive ink technology is to print RFID tag antennas. However, the printed RFID antennas, manufactured by conductive silver ink which is generally based on microsized silver particles, have lower conductivity and consequently lower radiation efficiency than those by conventional copper etching method. This work demonstrates nano-particle conductive silver ink that is capable of printing UHF RFID antennas with improved radiation efficiency. Compared with commercial micro-particle silver ink, the solid content of metal is much higher in the proposed nanoparticle silver ink, leading to better electrical properties. Two types of dipole antennas are printed with the proposed nano-particle as well as with commercial micro-particle inks. Also, the same antennas are fabricated by copper etching. With these conductive inks, a straight and a meandered dipole antennas are fabricated and their radiation efficiencies are measured with the Wheeler cap method. Experimental results show that the radiation efficiencies of the antennas based on nanoparticle silver ink are superior to those printed with the micro-particle silver ink, and are comparable to those of popular copper antennas.     

Characterization of lithographically printed resistive strain gauges

This paper reports progress in sensor fabrication by the conductive lithographic film (CLF) printing process. Work describing strain-sensitive structures manufactured using a modified printing process and conductive inks is addressed. The performance of a "single-ink" strain-sensitive structure when printed on six alternative substrates (GlossArt, PolyArt, Teslin, Mylar C, Melinex, and Kapton) is analyzed. Though not intending to compete with conventional gauges in high-tolerance measurement, the structures exhibit properties that indicate suitability for novel applications.     

Additive-Free Aqueous MXene Inks for Thermal Inkjet Printing on Textiles

Direct printing of functional inks onto flexible substrates allows for scalable fabrication of wearable electronics. However, existing ink formulations for inkjet printing require toxic solvents and additives, which make device fabrication more complex, limit substrate compatibility, and hinder device performance. Even water-based carbon or metal nanoparticle inks require supplemental surfactants, binders, and cosolvents to produce jettable colloidal suspensions. Here, a general approach is demonstrated for formulating conductive inkjet printable, additive-free aqueous Ti₃C₂T_x MXene inks for direct printing on various substrates. The rheological properties of the MXene inks are tuned by controlling the Ti₃C₂T_x flake size and concentration. Ti₃C₂T_x-based electrical conduits and microsupercapacitors (MSCs) are printed on textile and paper substrates by optimizing the nozzle geometry for high-resolution inkjet printing. The chemical stability and electrical properties of the printed devices are also studied after storing the devices for six months under ambient conditions. Current collector-free, textile-based MSCs show areal capacitance values up to 294 mF cm⁻² (2 mV s⁻¹) in poly(vinyl alcohol)/sulfuric acid gel electrolyte, surpassing reported printed MXene-based MSCs and inkjet-printed MSCs using other 2D nanomaterials. This work is an important step toward increasing the functional capacity of conductive inks and simplifying the fabrication of wearable textile-based electronics.     

导热高分子材料在包装印刷领域的研究进展

目的综述导热高分子材料在包装印刷领域的应用及研究现状,拓展导热高分子材料的应用领域。方法首先介绍2类导热高分子材料的制备方法,即本征型和填充型导热高分子材料;其次全面综述用于包装印刷领域的导热膜/纸、导热胶黏剂和导热油墨;最后总结常用的各类导热机理模型。结果与本征型导热高分子相比,填充型导热高分子具有加工简单、成本低廉、应用面广等优点,是目前研究最多的导热高分子材料。导热膜/纸、导热胶黏剂和导热油墨具有广泛的研究基础,市场需求旺盛。导热预测模型虽能够有效预测复合材料的热导率,但会受到填料含量和粒子形貌的影响。结论导热高分子材料在包装印刷领域拥有巨大的应用需求,开展导热高分子的研究具有重要的现实和理论意义。     

The research of manufacture of flexible conductive tracks at room temperature

Nano silver is widely used in conductive lines for its advantages, nano size, low melt temperature and excellent conductivity. In general, nano silver of less than 50 nm need be sintered at 200 centigrade in order to acquire conductivity, but it limits the choice of the substrates, only high temperature resistant substrate can be used, for example, PI film and glass. In order to acquire flexible tracks with excellent conductivity at room temperature on paper and PET, nano silver emulsion of 2 percent silver content was prepared through liquid phase chemical reduction, and then the concentration of silver was improved to 17 percent by centrifuging at high speed. And the emulsion was adjusted to meet the demand of inkjet printing, such as surface tension, and viscosity, pH value, then was jetted onto photo paper and PET film. High conductivity was acquired after treated by 830 nm infrared laser, and the sheet resistance is less than 2 omega/(see symbol). After aging test, the conductivity was stable. The method can be used in solar cells, flexible LED, intelligent packaging and can replace the traditional screen printing method at low cost.     

Hybrid 3D Printing of Soft Electronics

Hybrid 3D printing is a new method for producing soft electronics that combines direct ink writing of conductive and dielectric elastomeric materials with automated pick‐and‐place of surface mount electronic components within an integrated additive manufacturing platform. Using this approach, insulating matrix and conductive electrode inks are directly printed in specific layouts. Passive and active electrical components are then integrated to produce the desired electronic circuitry by using an empty nozzle (in vacuum‐on mode) to pick up individual components, place them onto the substrate, and then deposit them (in vacuum‐off mode) in the desired location. The components are then interconnected via printed conductive traces to yield soft electronic devices that may find potential application in wearable electronics, soft robotics, and biomedical devices.     

Properties of polyacrylic acid-coated silver nanoparticle ink for inkjet printing conductive tracks on paper with high conductivity

Silver nanoparticles with a mean diameter of approximately 30 nm were synthesized by reduction of silver nitrate with triethanolamine in the presence of polyacrylic acid. Silver nanoparticle-based ink was prepared by dispersing silver nanoparticles into a mixture of water and ethylene glycol. The mechanism for the dispersion and aggregation of silver nanoparticles in ink is discussed. The strong electrostatic repulsions of the carboxylate anions of the adsorbed polyacrylic acid molecules disturbed the aggregation of metal particles in solutions with a high pH value (pH > 5). An inkjet printer was used to deposit this silver nanoparticle-based ink to form silver patterns on photo paper. The actual printing qualities of the silver tracks were then analyzed by variation of printing passes, sintering temperature and time. The results showed that sintering temperature and time are associated strongly with the conductivity of the inkjet-printed conductive patterns. The conductivity of printed patterns sintered at 150 °C increased to 2.1 × 10⁷ S m⁻¹, which was approximately one third that of bulk silver. In addition, silver tracks on paper substrate also showed better electrical performance after folding. This study demonstrated that the resulting ink-jet printed patterns can be used as conductive tracks in flexible electronic devices.