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.     

Pollution-preventing anionic lithographic inks

Lithographic printing presses use aliphatic and aromatic solvents for cleaning various surfaces, which are coated with the ink. The conventional printing inks also contain volatile solvents. During printing and cleaning operations, volatile organic compounds (VOCs) present in the inks and cleaning solvents are lost to the atmosphere by evaporation and these losses are quantifiable and alarmingly high. A new type of ink based on castor oil, which completely eliminates emissions of VOCs, has been developed. Synthesis of resins and the kinetics of washing of the ink, similar to the recently announced pollution-preventing ink [development of a VOC-free lithographic printing system. TAGA Proc., 324], with water at a slightly elevated pH are studied. A correlation between the mass-transfer coefficient characterizing the washing of ink and the experimental process variables is confirmed. New data are also reported on flake-formation dynamics.     

Fire-through Ag contact formation for crystalline Si solar cells using single-step inkjet printing

Inkjet-printed Ag metallization is a promising method of forming front-side contacts on Si solar cells due to its non-contact printing nature and fine grid resolution. However, conventional Ag inks are unable to punch through the SiN(x) anti-reflection coating (ARC) layer on emitter Si surfaces. In this study, a novel formulation of Ag ink is examined for the formation of fire-through contacts on a SiN(x)-coated Si substrate using the single-step printing of Ag ink, followed by rapid thermal annealing at 800 degrees C. In order to formulate Ag inks with fire-through contact formation capabilities, a liquid etching agent was first formulated by dissolving metal nitrates in an organic solvent and then mixing the resulting solution with a commercial Ag nanoparticle ink at various volume ratios. During the firing process, the dissolved metal nitrates decomposed into metal oxides and acted in a similar manner to the glass frit contained in Ag pastes for screen-printed Ag metallization. The newly formulated ink with a 1 wt% loading ratio of metal oxides to Ag formed finely distributed Ag crystallites on the Si substrate after firing at 800 degrees C for 1 min.     

Control of the Surface Morphology of Ceramic/Polymer Composite Inks for Inkjet Printing

The use of organic/inorganic composite inks in the Drop on Demand inkjet printing technology is a promising as well as demanding approach for the fabrication of composite thick films. Therefore, a versatile ceramic/polymer composite ink system for inkjet printing is developed in this study, containing Ba_0.6Sr_0.4TiO₃ (BST) and poly(methyl methacrylate) (PMMA). When developing such inks suitable for a one‐step fabrication, the major challenge is to fulfill the requirements of the inkjet printing technology and to obtain homogeneous surface morphologies after drying. Thus, possible influencing factors like the solvent composition, the solids content, and the ratio of ceramic to polymer are investigated to obtain a detailed knowledge for the general ink development. The fluid mechanical properties, viscosity, density, and surface tension are characterized. The main focus of this study lies on the drying behavior of the different inks, with the interactions of the ceramic particles, and the dissolved polymer molecules being highlighted. Furthermore, the drying behavior depending on the ink composition is shown. This study provides new insights into the possibility of using composite inks for the inkjet printing process and the fabrication of printed composite thick films in a single process step.

     

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.     

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。     

喷印工艺控制参数对水性油墨墨滴形态的影响

目的为了提高水性油墨的喷墨印刷质量,通过控制喷印工艺参数以获得良好的墨滴形态。方法分析喷印工艺控制的关键参数以及墨滴形态的表征参数,通过单因素工艺参数对墨滴形态影响的实验,分析电压、点火频率和脉冲宽度对墨滴形态各评价指标的影响程度,并运用AHP法构建墨滴形态的质量分析模型;通过多因素工艺参数组合对墨滴形态影响的正交实验,分析各工艺参数与墨滴形态参数之间的关联性,并结合质量评价模型综合评判喷印工艺参数对墨滴形态的影响。结果喷印工艺参数电压、点火频率和脉冲宽度共同影响墨滴形态的质量,脉冲宽度对其影响最大,点火频率次之,电压的影响程度最小,其权重分别为0.462,0.272,0.266。结论水性油墨喷印工艺中,通过合理地控制喷印工艺的关键参数,可以有效地提高墨滴形态质量,从而获得良好的印刷品质量。     

Printing with Satellite Droplets

Despite their specific methodologies, all current noncontact printing techniques such as inkjet printing (IJP), involve the break‐up of a liquid meniscus during the separation of the ink droplet from the bulk ink reservoir. Often, the break‐up of a liquid meniscus results in the formation of one or more satellite droplet whose volumes are several orders of magnitude smaller than the primary droplet. Many attempts are directed to suppress or control the formation of satellite droplets because they blur the printing result. For the first time, a simple mechanism by which a single satellite droplet is exclusively formed and directed to the substrate by a gas stream while the primary droplet remains attached to a metal rod used for controlling the formation and break‐up of the meniscus is reported. High printing resolution is demonstrated by satellite droplets printing (SDP) without the need for small orifices which are prone to clogging. Furthermore, the droplet generation from a large orifice enables SDP to handle viscous inks which has remained challenging for traditional IJP.     

多色打印中基于光谱的油墨选择——最佳油墨选择

描述了从给定油墨库中选择出一组八色油墨,建立最小化同色异谱的八色光谱打印模型的油墨选择算法.对于一个含有n种油墨的油墨库,这里有Cn8种油墨组合,当n很大时,油墨组合的数量就成了几何数字.有些明显不可能的油墨组合,通过解析法可以去除.首先,使用向量相关性分析法来去除没有可行性的组合.然后,用连续调相似评估每一备选油墨组的色度和光谱精确度.选择备选油墨组中对应有光谱精确度最高的一组油墨,定为八色打印过程的最佳油墨组以获取最小同色异谱的色彩复制.     

Rheological properties and screen printability of UV curable conductive ink for flexible and washable E-textiles

As a critical component for the realization of flexible electronics,multifunctional electronic textiles(etextiles)still struggle to achieve controllable printing accuracy,excellent flexibility,decent washability and simple manufacturing.The printing process of conductive ink plays an important role in manufacturing e-textiles and meanwhile is also the main source of printing defects.In this work,we report the preparation of fully flexible and washable textile-based conductive circuits with screen-printing method based on novel-developed UV-curing conductive ink that contains low temperature and fast cure features.This work systematically investigated the correlation between ink formulation,rheological properties,screen printability on fabric substrates,and the electrical properties of the e-textile made thereafter.The rheological behaviors,including the thixotropic behavior and oscillatory stress sweep of the conductive inks was found depending heavily on the polymer to diluent ratio in the formulation.Subsequently,the rheological response of the inks during screen printing showed determining influence to their printability on textile,that the proper control of ink base viscosity,recovery time and storage/loss modulus is key to ensure the uniformity of printed conductive lines and therefore the electrical conductivity of fabricated e-textiles.A formulation with 24 wt%polymer and 10.8 wt%diluent meets all these stringent requirements.The conductive lines with 1.0 mm width showed exceptionally low resistivity of 2.06×10^-5Ωcm Moreover,the conductive lines presented excellent bending tolerance,and there was no significant change in the sample electrical resistance during 10 cycles of washing and drying processes.It is believed that these novel findings and the promising results of the prepared product will provide the basic guideline to the ink formulation design and applications for screen-printing electronics textiles.     

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.     

Characterization of inks and ink application for ink-jet printing: model and simulation

Ink-jet printing quality is determined primarily by, among other factors, the printing engine and its inks. The printing engine controls the process of ink application and the scheme of ink mixing for th e generation of secondary and tertiary colors. The inks selectively absorb different wavelengths from the illumination and result in the visible color output. Therefore characterizations of the output print in terms of ink distribution and volume, the scheme of ink mixing, light absorption, and light scattering are of essential importance in controlling and understanding the quality of the color reproduction. I present a method to characterize the ink volume and the properties of the ink by means of spectral reflectance measurements and simulations. The simulations are based on the Kubelka-Munk theory, whose applicability to ink-jet printing is also discussed.     

Organic/polymeric electroluminescent devices processed by hybrid ink-jet printing

Ink-jet printing (IJP) technology is a popular technology for desktop publishing. Since some of the conducting (or conjugated) organic molecules and polymers are solution processable, IJP becomes an ideal method for printing polymer/organic light-emitting diodes with high resolution. In this review article, we present the hybrid ink-jet printing technology (HIJP), which consists of an ink-jet printed layer in conjunction with another uniform spin-coated polymer layer, which serves as a buffer layer to seal the pin holes between the ink droplets. This HIJP technology has been successfully applied to the fabrication of polymer light-emitting logos, multicolor polymer/organic light-emitting diodes, and the built-in shadow mask for the cathode patterning for pixelated polymer LEDs.     

丙烯酸酯对水性聚氨酯乳液及其塑料凹版油墨的性能的影响

采用乳液共聚法制备了聚氨酯-聚丙烯酸酯(PUA)复合乳液,并以酞菁蓝为颜料配制了塑料凹版水性油墨,讨论了乙烯基单体甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)对PUA 乳液及其水性油墨的性能的影响.结果表明,随着MMA含量的增加,PUA复合乳液的粘度先减小然后增大.随着m(BA)/m(MMA)的增加,PUA乳液的粘度先变大随后减小.用固含量为30%(质量分数,后同)的PUA乳液配制的水性油墨的粘度随时间推移而增大.水性油墨的初干性随MMA与聚氨酯(PU)的质量比的增加而变好,但随着m(BA)/m(MMA)的增加而变差.当MMA与PU的质量比达到0.25后,水性油墨不仅对PET薄膜具有优异的附着牢度,对OPP薄膜也有良好的附着牢度,同时具有良好的耐水耐酸性能.     

Printed antennas with variable conductive ink layer thickness

One of the complex tasks in mass production of RF electronics is printing the communication antenna using electrically conductive ink. For example, this is very common for radio- frequency identification (RFID) tags. Electrical properties of the ink are mostly determined by conductive (e.g. silver) particles mixed into the ink solution and the way they `connect' in the cured ink. It is also desirable to minimise the amount of ink used per antenna, because high-conducting metals like silver used in the ink are rather expensive. Metal-based inks have limited conductivity, so the thicker the cured ink layer will be the better the antenna radiation efficiency can be achieved, but also the higher will be the costs. In the paper, the authors report on the investigations of the possibility of minimising the amount of ink used per antenna. This can be achieved by printing thicker ink layers, where antenna structures are known to have high current density. Two common antenna structures and a dedicated antenna for passive RFID are used in the investigation. The main result of the paper is that radiation efficiency depends primarily on the total amount of ink used for printing the antenna, rather than on the variations of the layer thickness within the antenna structure     

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.     

有机相脱酸体系对不同老化墨迹的影响

目的 为了评价古籍化学品的综合效果,完善其除纸张性能外的墨迹的评价指标,探究不同有机相脱酸体系对老旧书页墨迹的影响.方法 制备胶印、中性笔墨样和书法用墨样,并对墨样进行人工老化处理.选择氢氧化钡的甲醇溶液(质量浓度为20 g/L)、氢氧化钡的二乙二醇溶液(质量浓度为17 g/L)和碳酸镁的甲醛溶液(质量浓度为10 g/L)分别对老旧书页以及人工老化的墨样进行脱酸处理.通过扫描仪高分辨率扫描墨样进行图像观察,用分光光度计测量墨样色密度,对3种有机相脱酸剂处理后的墨迹效果进行主客观评价.结果 主客观评价结果显示,经氢氧化钡的甲醇溶液处理后的墨样变化轻微;经碳酸镁的甲醛溶液处理后,墨样表面覆有1层碳酸镁颗粒,墨迹颜色明显变浅,墨样色密度显著降低;经氢氧化钡的二乙二醇溶液处理后,墨迹颜色变深,墨样色密度和线宽均有所增加.结论 不同脱酸体系会对老化墨样字迹产生不同程度影响,研究从图文信息质量的角度为古籍脱酸化学品的综合效果与评价提供一定的参考和借鉴.     

Water-reducible flexographic printing inks—rheological behaviour and interaction with paper substrates

The rheological behaviour of 5 water-reducible flexographic printing inks was tested using viscometer with the cone and plate geometry. The obtained shear stress versus shear rate curves for the original inks, and additionally, for the mixtures with various amount of added water, exhibit pseudoplastic behaviour, and were successfully fitted by Ostwald and Casson models. The viscosity of printing inks after addition of water was tested also by means of outflow funnel. The transfer of flexographic inks on the different paper substrates was examined by optical density measurements. The density curves confirmed that the ink concentration above 50 wt% is sufficient to obtain the constant value of optical density. The best ink transfer to the investigated paper substrates was observed for folding carton characterized by the high value of smoothness.     

胶印印刷压力对油墨转移性能的影响

目的研究不同印刷压力下CMYK四色油墨的油墨转移率的变化趋势。方法采用控制变量法对胶印印刷压力和油墨转移之间的关系进行深入研究,运用IGT C1-5印刷适性仪印刷胶版纸,印刷速度相同,在不同的印刷压力下进行实验。结果得到了CMYK 4种油墨不同印刷压力下在胶版纸上印刷的油墨转移率数据,利用Matlab软件对所得数据进行拟合,得到了印刷压力与油墨转移率的关系曲线和方程。结论油墨转移率随印刷压力的增加而显著增大,在胶版纸上印刷压力达到450 N左右时,油墨转移率最大,随后油墨转移率随着印刷压力的增加而降低。经软件分析油墨转移率和印刷压力呈五次曲线关系。     

喷墨打印技术在功能材料精密器件加工中的应用

喷墨打印技术应用于聚合物成膜或成型,已成为功能聚合物沉积和精密器件加工领域的核心技术之一。介绍了喷墨打印技术在聚合物电致发光器件、有机薄膜晶体管、太阳能电池和传感器等领域的研究和应用进展,包括聚合物墨水的制备、薄膜均匀性、聚合物溶液与打印性能的关系、新型功能材料的研究和开发等问题,并指出了存在的问题和面临的挑战。