Inkjet printing of Ce<Subscript>0.8</Subscript>Gd<Subscript>0.2</Subscript>O<Subscript>2</Subscript> thin films on Ni-5%W flexible substrates

The successful inkjet printing of a cerium gadolinium oxide (Ce_0.8Gd_0.2O₂) precursor solution on highly textured Ni-5%W is reported. A stable ink was synthesised from metal acetates and propionic acid with rheological properties suitable for inkjet printing and also the development of solid–liquid interface comparable with thin film formation by dip coating. Two different drop-on-demand print heads were used for deposition: a 16-nozzle piezoelectric cartridge and a single electromagnetic nozzle. Two different rastering patterns with different droplet sizes and spacing were compared. Thermogravimetry and X-ray diffractometry were used to study the thermal decomposition of the metal oxide precursors and to determine the shortest possible heat treatment of the deposited layers, potentially suitable for continuous large scale production. The results from X-ray diffraction show that the single phase Ce_0.8Gd_0.2O₂ was obtained in all cases, but only piezoelectric inkjet printing with optimised drop overlapping produces a highly textured buffer layer. Optical micrographs and atomic force microscopy also indicate the good quality of deposited films after heat treatment.     

Synthesis of nanoparticle-cored dendrimers by convergent dendritic functionalization of monolayer-protected nanoparticles

This article presents a synthesis method for nanoparticle-cored dendrimers (NCDs), which have dendritic architectures around a monolayer-protected gold nanoparticle. The synthesis method is based on a strategy in which the synthesis of monolayer-protected nanoparticles is followed by adding dendrons on functionalized nanoparticles by a single coupling reaction. NMR spectroscopy, IR spectroscopy, and thermogravimetric analysis (TGA) characterizations confirmed the successful coupling reaction between dendrons with different generations ([G1], [G2], and [G3]) and COOH-functionalized nanoparticles ( approximately Au201L71). The dendrimer wedge density also could be controlled by reacting nanoparticles having different loading of COOH groups ( approximately 60 and approximately 10% COOH of the 71 ligands per gold nanoparticle) with functionalized dendrons. Transmission electron microscope results showed that this synthesis strategy maintains the average size of the nanoparticle core during dendron coupling reactions. This control over the composition and core size makes the systematic study of NCDs with different generations possible. The chemical stability of NCDs was found to be affected by dendron generation around the nanoparticle core. The current-potential response of NCD films on microelectrode arrays exhibited better electrical conductivity for NCDs with lower dendron generation.     

数字喷墨印刷关键技术及其实现

经过20多年的完善与发展，喷墨技术已经成为大幅面广告印刷行业的主要印刷技术。随着图书按需印刷需求的快速扩张以及国家环保政策的迅速落地，喷墨印刷技术作为一项高效环保的数字化印刷技术，得到越来越高的关注，业内普遍认为喷墨印刷技术将是数字化印刷的必然发展趋势。然而与已经成熟的多Pass喷墨印刷设备不同，单Pass喷墨印刷设备在数据带宽、数据在线重构、高精度同步控制、喷嘴在线补偿等方面有着极高的技术要求。本文首先简要介绍了喷墨技术，然后针对单Pass喷墨印刷设备需要解决的技术问题提出了相应的解决方案。依据本文技术设计的单Pass书刊喷墨印刷机已经投放市场，并且获得了用户的普遍认可。     

Inkjet printing of well-defined polymer dots and arrays

Inkjet printing represents a highly promising polymer deposition method, which is used for, for example, the fabrication of multicolor polyLED displays and polymer-based electronics parts. The challenge is to print well-defined polymer structures from dilute solution. We have eliminated the formation of ring stains by printing nonvolatile acetophenone-based inks on a perfluorinated substrate using different polymers. (De)pinning of the contact line of the printed droplet, as related to the choice of solvent, is identified as the key factor that determines the shape of the deposit, whereas the choice of polymer is of minor importance. Adding 10 wt % or more of acetophenone to a volatile solvent (ethyl acetate)-based polymer solution changes the shape of the deposit from ring-like to dot-like, which may be due to the establishment of a solvent composition gradient. Arrays of closely spaced dots have also been printed. The size of the dots is considerably smaller than the nozzle diameter. This may prove a potential strategy for the inkjet printing of submicrometer structures.     

Inkjet-printed thiol self-assembled monolayer structures on gold: quality control and microarray electrode fabrication

Laterally structured, self-assembled monolayers (SAMs) of different thiols (HS-R-X, R = (CH 2) 3-16, X = -CH 3, -COOH, -NH 2) on gold have been prepared by inkjet printing. The printer is a modified, low-cost desktop printer (Epson Stylus Photo R200), the ink is a 1 mM solution of the thiol in ethanol/glycerol (6:1). The quality of inkjet-printed large area SAMs obtained in this study is between that of a layer self-assembled from a thiol solution and that obtained by soft lithography, according to cyclic voltammetry, electrochemical impedance spectroscopy, scanning electrochemical microscopy (SECM), and polarization-modulated Fourier transform infrared reflection-absorption spectroscopy (PM IRRAS). For the first time, simultaneous printing of two different thiols in a single print job as an alternative to sequential printing and backfilling is demonstrated. The smallest structures consisting of conductive disks of 40 microm diameter were analyzed as single spots by SECM and as random array electrodes with different average disk-disk distance. Conductive band electrodes with variable bandwidth (300 microm to 1 cm) are presented, as well as a pH switchable band structure. As compared to stamping, inkjet printing allows for simultaneous multiple thiol printing in a single print job with the resolution limited only by the droplet size and the precision of the translation stage.     

Nanoinks in inkjet metallization — Evolution of simple additive-type metal patterning

Recent advances in the development of stable dispersions of nanophase metal particles have allowed the direct fabrication of metal patterns (e.g., printed circuits, RFID tags, touch screens, etc.) by simple additive type inkjet processes. Such processes replace the more costly and less environmentally friendly subtractive lithographic type photoprocesses involving selective etching of photoresists and metal layers and more complex additive type process using photocatalysts for patterned metal deposition by electroless plating processes and inkjet patterning of metal catalyst or catalyst precursor for subsequent metallization by electroless plating. The recent development of electrohydrodynamic jet printing (e-jet printing), in which the ink drop is ejected under the influence of an electric field, has allowed a significant resolution increase vs. conventional inkjet printing with a piezoelectric head (printing resolution of ca. 100 nm for e-jet printing vs. ca. 20 μm for inkjet printing).     

Inkjet-printed monolayers as platforms for tethered polymers

Combining inkjet printing and atom-transfer radical polymerization (ATRP) provides a straightforward and versatile method for producing patterned polymer surfaces that may serve as platforms for a variety of applications. We report the use of drop-on-demand technology to print binary chemical gradients and simple patterns onto solid substrates and, by using surface-confined ATRP, amplify these patterns and gradients. Chemically graded monolayers prepared by inkjet printing dodecanethiol and backfilling with 11-mercaptoundecanol showed continuous changes in the water contact angle along the gradient. These samples also exhibited a distinct change in the intensity of methyl group and C-O stretching modes along the gradient. Graded or patterned polymer layers were produced by growing, with ATRP, tethered poly(methyl methacrylate) (PMMA) layers from gradient or patterned printed monolayers that contained a bromo-capped initiator. Atomic force microscopy and optical microscopy confirmed that the PMMA layers amplified the underlying printed initiator layer with remarkable fidelity.     

Paper‐Based Inkjet‐Printed Microfluidic Analytical Devices

Rapid, precise, and reproducible deposition of a broad variety of functional materials, including analytical assay reagents and biomolecules, has made inkjet printing an effective tool for the fabrication of microanalytical devices. A ubiquitous office device as simple as a standard desktop printer with its multiple ink cartridges can be used for this purpose. This Review discusses the combination of inkjet printing technology with paper as a printing substrate for the fabrication of microfluidic paper‐based analytical devices (μPADs), which have developed into a fast‐growing new field in analytical chemistry. After introducing the fundamentals of μPADs and inkjet printing, it touches on topics such as the microfluidic patterning of paper, tailored arrangement of materials, and functionalities achievable exclusively by the inkjet deposition of analytical assay components, before concluding with an outlook on future perspectives.     

Spreading of an inkjet droplet on a solid surface with a controlled contact angle at low Weber and Reynolds numbers

Even though the inkjet technology has been recognized as one of the most promising technologies for electronic and bio industries, the full understanding of the dynamics of an inkjet droplet at its operating conditions is still lacking. In this study, the normal impact of water droplets on solid substrates was investigated experimentally. The size of water droplets studied here was 46 microm and was much smaller than the most of the previous studies on drop impact. The Weber number (We) and Reynolds number (Re) were 0.05-2 and 10-100, respectively, and the Ohnesorge number was fixed at 0.017. The wettability of the solid substrate was varied by adsorbing a self-assembled monolayer of octadecyltrichlorosilane followed by the exposure to UV-ozone plasma. The impact scenarios for low We impacts were found to be qualitatively different from the high to moderate We impacts. Neither the development of a thin film and lamella under the traveling sphere nor the entrapment of small bubbles was observed. The dynamics of droplet impact at the conditions studied here is found to proceed under the combined influences of inertia, surface tension, and viscosity without being dominated by one specific mechanism. The maximum spreading factor (beta), the ratio of the diameter of the wetted surface and the drop diameter before impact, was correlated well with the relationship ln beta=0.090 ln We/(fs-cos theta)+0.151 for three decades of We/(fs-cos theta), where theta is the equilibrium contact angle, and fs is the ratio between the surface areas contacting the air and the solid substrate. The result implies that the final shape of the droplet is determined by the surface phenomenon rather than fluid mechanical effects.     

Liquid–paper interactions during liquid drop impact and recoil on paper surfaces

The spreading and recoiling of water drops on several flat and macroscopically smooth model surfaces and on sized paper surfaces were studied over a range of drop impaction velocities using a high-speed CCD camera. The water drop spreading and recoiling results on several model hydrophobic and hydrophilic surfaces were found to be in agreement with observations reported in the literature. The maximum drop spreading diameter for those model surfaces at impact was found to be dependent upon the initial drop kinetic energy and the degree of hydrophobicity/hydrophilicity of the surface. The extent of the maximum drop recoiling was found to be much weaker for hydrophilic substrates than for hydrophobic substrates. Sized papers, however, showed an interesting switch of behaviour in the process of water drop impaction. They behave like a hydrophobic substrate when a water drop impacts on it, but like a hydrophilic substrate when water drop recoils. Although the contact angle between water and hydrophilic or hydrophobic non-porous surfaces changes from advancing to receding as reported in literature, the change of contact angle during water impact on paper surface is unique in that the level of sizing was found to have a smaller than expected influence on the degree of recoil. Atomic force microscopy (AFM) was used to probe fibres on a sized filter paper surface under water. The AFM data showed that water interacted strongly with the fibre even though the paper was heavily sized. Implications of this phenomenon were discussed in the context of inkjet print quality and of the surface conditions of sized papers. Results of this study are very useful in the understanding of inkjet ink droplet impaction on paper surfaces which sets the initial condition for ink penetration into paper after impaction.     

基于高光谱成像结合分光光度技术的喷墨打印墨水种类鉴别方法

在法庭科学实践中,往往需要通过对文件中字迹墨水的成分分析来精确地判定检材和样本文件的同一性。利用高光谱成像和分光光度技术结合化学计量法,提出了一种对喷墨打印墨水分类的方法。采集14台不同品牌、型号的四色喷墨打印墨水高光谱数据和色度值。计算出平均色度值后进行PCA降维处理和K-Means聚类分析,将样品初步分类。之后应用LightGBM模型、XGBoost模型和SVM模型共三种分类模型,以1:4的比例确定测试集和训练集,对聚类分析结果中每一类别的样品进行逐一鉴别。结果表明,LightGBM和XGBoost对四色样品的分类精度都能达到95%以上,SVM的分类精度为100%。提出的方法能够做到无损、准确、快速地将不同品牌乃至型号的喷墨打印墨水进行区分。     

Fabrication of polymer microsphere particle standards containing trace explosives using an oil/water emulsion solvent extraction piezoelectric printing process

We present a methodology for fabricating polymer microspheres using inkjet printing of a biodegradable polymer containing either high explosives or high explosive simulant. Poly(dl-lactide/glycolide) 85:15 (PLGA) microsphere production is based on an oil/water emulsion solvent extraction process. The inkjet printing process allows for precise control of the microsphere diameter and the chemical composition. The microspheres can be used as calibrants or verification standards for explosives trace detection instruments. Gas chromatography/mass spectrometry analysis demonstrated that the composition of the microspheres was consistent with predicted concentrations based on the amount of analyte incorporated into the polymer solution and the inkjet operating parameters. We have demonstrated that the microspheres can be fabricated with a mass fraction of 70% of an analyte compound.     

喷墨打印图案化高分子薄膜及其在有机电子器件加工中的应用

喷墨打印技术由于在图案化加工方面的高效、低成本、非接触形式及柔性的加工过程等特点而被应用于有机电子器件的加工中.通过打印功能性高分子溶液,喷墨打印实现了功能高分子薄膜的沉积和图案化,并实现了有机发光二极管、有机薄膜晶体管及其集成器件的加工.对喷墨打印在有机电子器件加工中取得的成果进行了总结,同时综述了高分子溶液喷墨打印过程中存在的基本科学问题和研究现状.     

Metal-core--organic shell dendrimers as unimolecular micelles

The synthesis and characterization of nanoparticle-cored dendrimers (NCDs), consisting of a metal core capped by arylpolyethers terminated with ester or carboxylate groups, are reported. These NCDs, comprising nanometer-sized gold clusters at the core and organic dendrons radially connected to the gold core by gold-sulfur bonds, were analyzed by TEM, TGA, UV, IR, and NMR spectroscopies. The density of the branching units connected to the core decreased from 1.90/nm(2) for a first-generation NCD (Au-G1(CO(2)Me)) to 0.80/nm(2) for a fourth-generation NCD (Au-G4(CO(2)Me)). Although the ester-terminated NCDs were stable and resisted aggregation, they were easily hydrolyzed to the corresponding water-soluble sodium salts. Aqueous solutions of (Au-Gn(CO(2)Na)) exhibited micellar properties. Since these NCDs possess a relatively unpassivated metal core and an organic aryl ether shell with micellar and dendritic properties, they are expected to have important potential applications in catalysis.     

The effects of coil-stretch transition behavior of polyfluorene inks on single droplet formation during inkjet printing

For drop-on-demand (DOD) inkjet printing, stable and single ink droplet formation without satellite dots is the key to improve the print quality. The formation of stable and single droplet is influenced by filament break up and the polymer chain's coil-stretch transition behavior. In this paper, the droplet formation behaviors of polyfluorene (PFO) ink at various driving voltages (V), polymer chain's coil-stretch transition mechanism and its effects on single ink droplet formation are investigated. It indicates that when 58 < V ≤ 63 V, a single and stable droplet is formed with a pulse time of 38.5 μs. At this stage, the Weissenberg number (Wi) < 0.5, the PFO molecular chain is coiled to guarantee stable and single droplets. When V > 63 V, Wi > 0.5, the PFO molecular chain is stretched because of the high hydrodynamic forces, resulting unwanted satellite droplets. When 55 < V ≤ 58 V, the droplet shrinks into the nozzle, which indicates that the kinetic energy supplied by the deformation of the piezoelectric transducer isn't enough to force the droplet to be jetted from the nozzle.     

Competing fracture in kinetically controlled transfer printing

Transfer printing by kinetically switchable adhesion to an elastomeric stamp shows promise as a powerful micromanufacturing method to pickup microstructures and microdevices from the donor substrate and to print them to the receiving substrate. This can be viewed as the competing fracture of two interfaces. This paper examines the mechanics of competing fracture in a model transfer printing system composed of three laminates: an elastic substrate, an elastic thin film, and a viscoelastic member (stamp). As the system is peeled apart, either the interface between the substrate and thin film fails or the interface between the thin film and the stamp fails. The speed-dependent nature of the film/stamp interface leads to the prediction of a critical separation velocity above which separation occurs between the film and the substrate (i.e., pickup) and below which separation occurs between the film and the stamp (i.e., printing). Experiments verify this prediction using films of gold adhered to glass, and the theoretical treatment extends to consider the competing fracture as it applies to discrete micro-objects. Temperature plays an important role in kinetically controlled transfer printing with its influences, making it advantageous to pickup printable objects at the reduced temperatures and to print them at the elevated ones.     

Interfacial oil droplets

Very small, discrete oil droplets can form at the solid-liquid interface. We demonstrate this effect through formation of decane droplets at the interface between an aqueous ethanol solution and silicon wafers that have been made hydrophobic through self-assembly of octadecyltrichlorosilane (OTS). The droplets have a lens-like shape; the shape is approximately a spherical cap with a contact angle < 25 degrees. The heights of the droplets are about 2-50 nm, and diameters at the three-phase boundary are about 100-600 nm in 25% ethanol solution. The size and contact angle can be varied by changing the ethanol concentration. The contact angle of the very small droplets (height < 20 nm) is similar to the contact angle of macroscopic droplets (height approximately equal to 1 mm), so the line tension is very small. The droplets are only stable for a few hours: they gradually lose mass, presumably through Ostwald ripening. The drop perimeter is not pinned during ripening but retreats across the solid. We form the droplets by direct adsorption from an emulsion; evidence for adsorption is obtained by comparing the drop volumes in bulk to the volumes at the interface. The droplet sizes are obtained by dynamic light scattering and atomic force microscopy.     

Synthesis and Characterization of Gold‐Nanoparticle‐Cored Dendrimers Stabilized by Metal–Carbon Bonds

Synthesis and characterization of gold‐nanoparticle‐cored dendrimers (NCDs), in which the dendrons are attached to the gold core through gold–carbon bonds, are described. Synthesis of these materials involved the simultaneous reduction of HAuCl₄ and a Fréchet‐type dendron with a diazonium group at the focal point, all in an organic solvent such as toluene. These materials possess a nanometer‐sized gold core surrounded by a shell of polyaryl ether dendrons, which are connected radially to the core. The NCDs were characterized by TEM, thermogravimetric analysis (TGA), and IR, UV, and NMR spectroscopic techniques. Average particle diameter of the NCDs ranged from 4.7 to 5.5 nm for the different generations. All NCDs exhibit the characteristic plasmon absorption of gold nanoparticles at 520 nm. Average numbers of dendrons per NCD in AuG_n were calculated using results from TGA and TEM studies. Multiple layering of the dendrons is proposed as a possible reason for the high dendron/NCD value.     

A new technique for the deposition of standard solutions in total reflection X-ray fluorescence spectrometry (TXRF) using pico-droplets generated by inkjet printers and its applicability for aerosol analysis with SR-TXRF

A new technique for the deposition of standard solutions on particulate aerosol samples using pico-droplets for elemental determinations with total reflection X-ray fluorescence spectrometry (TXRF) is described. It enables short analysis times without influencing the sample structure and avoids time consuming scanning of the sample with the exciting beam in SR-TXRF analysis. Droplets of picoliter volume (∼ 5–130 pL) were generated with commercially available and slightly modified inkjet printers operated with popular image processing software. The size of the dried droplets on surfaces of different polarity namely silicone coated and untreated quartz reflectors, was determined for five different printer types and ten different cartridge types. The results show that droplets generated by inkjet printers are between 50 and 200 μm in diameter (corresponding to volumes of 5 to 130 pL) depending on the cartridge type, which is smaller than the width of the synchrotron beam used in the experiments (< 1 mm at an energy of 17 keV at the beamline L at HASYLAB, Hamburg). The precision of the printing of a certain amount of a single element standard solution was found to be comparable to aliquoting with micropipettes in TXRF, where for 2.5 ng of cobalt relative standard deviations of 12% are found. However, it could be shown that the printing of simple patterns is possible, which is important when structured samples have to be analysed.     

Inkjet Printing of Polymer Micro‐Arrays and Libraries: Instrumentation,Requirements, and Perspectives

This article reviews commercially available instrumentation for inkjet printing of polymer micro‐arrays for combinatorial materials research, and requirements thereof. These include a print head positioning accuracy better than 10 μm and a minimum drop volume of 100 pL. Commercially available instruments that fulfill these requirements can be divided into two categories, depending on whether they receive ink from a reservoir (dispense mode) or through fluid aspiration (pipette mode). Instruments belonging to the first category are restricted to the preparation of polymer blend micro‐arrays. These consist of a few substances mixed in various ratios. The other instruments can be used for the preparation of both micro‐arrays of large numbers of different pure polymer compounds and polymer blend micro‐arrays. Moreover, ways to mix compounds are discussed.