A promising approach to conductive patterns with high efficiency for flexible electronics

A promising approach for conductive patterns with high efficiency for flexible electronics was developed by direct-writing, silver(I) solution (silver nitrate, acetate silver, etc.) with no solid particles as a conductive ink, conductive pen as a writing implement, and polyimide (PI) film as a substrate. The physical properties of the conductive ink were investigated by a dynamic contact angle system, ubbelohde viscometer and surface tension instrument. Conductive properties of silver ink film were investigated by 4-point probe, scanning electron microscope (SEM) and surface profilometer. It is demonstrated how the design of solvent composition in conductive ink affects surface morphology, and conductivity of silver ink films. It can be obtained that conductive patterns drawn on PI substrate not only have good mechanical/electrical fatigue properties, but also have low resistivity. Especially, when the sintering condition is 200 °C for 60 min, the resistivity can be down to 6.6 μΩ cm, 4.25 times the silver bulk resistivity.     

Novel materials for electronic device fabrication using ink-jet printing technology

Novel materials and a metallization technique for the printed electronics were studied. Insulator inks and conductive inks were investigated. For the conductive ink, the nano-sized copper particles were used as metallic sources. These particles were prepared from a copper complex by a laser irradiation process in the liquid phase. Nano-sized copper particles were consisted of a thin copper oxide layer and a metal copper core wrapped by the layer. The conductive ink showed good ink-jettability. In order to metallize the printed trace of the conductive ink on a substrate, the atomic hydrogen treatment was carried out. Atomic hydrogen was generated on a heated tungsten wire and carried on the substrate. The temperature of the substrate was up to 60 °C during the treatment. After the treatment, the conductivity of a copper trace was 3 μΩ cm. It was considered that printed wiring boards can be easily fabricated by employing the above materials.     

无颗粒型银导电墨水的制备及其印刷成膜研究

以柠檬酸银为导电金属前驱体化合物,仲丁胺为络合剂,并添加乙醇调节粘度和表面张力等物性参数,制备了无颗粒型银导电墨水。该导电墨水可以采用凹版印刷方式印刷在PET片基上,并且在较低的热处理温度下即可获得导电性较好的银导电膜。利用X射线光电子能谱仪、同步热分析仪、红外光谱仪、X射线衍射仪、扫描电子显微镜和四探针测试仪对柠檬酸银、导电墨水以及银导电膜进行表征。结果表明导电墨水在132 ℃时残留质量即达到恒重,远低于柠檬酸银的210 ℃;经150 ℃热处理之后,银导电膜由均匀致密、纯度高的纳米银颗粒组成;经150 ℃热处理50 min后得到的银导电膜的方块电阻值为1.83 Ω·□-1。     

Low temperature nanoparticle sintering with continuous wave and pulse lasers

New manufacturing methods are being sought for electronics production. Printable electronics is a promising method for producing low cost and large-scale electronics. In printable electronics nanoparticle inks printed on the surface of substrate contain additives, such as dispersing agent and carrier fluids that provide good printing properties by changing the viscosity and separating the nanoparticles of the ink. In the sintering process ink particles are heated to a certain, ink-specific temperature. During the sintering process the carrier fluid and dispersing agents are evaporated from the ink. Additional heating after evaporation causes the nanoparticles to start to agglomerate. A small particle size allows the use of a considerably lower sintering temperature than with bulk silver, for example 220 °C. The sintering process is usually utilized with a convection oven, with a long sintering time, and the thermal load on the surrounding material can become too great as components and patterns are formed from layers of different type inks. Hence, alternative sintering methods are sought. This paper describes tests done with two different types of laser; pulsed and continuous wave lasers. Laser sintering enables short sintering times and selective sintering, making it possible for printed structures to contain fragile active components produced with other technologies.     

Infra-red assisted sintering of inkjet printed silver tracks on paper substrates

In this study, conductive silver features using inkjet printing have been successfully prepared and their sintering studied. Regarding conductivity, metallic inks are the most efficient available conductive inks, even if important drawbacks regarding the use of such inks in inkjet still exist. Indeed, the sintering step is an important limiting factor for the productivity and the substrate choice. An infrared (IR) drying method was experimented to optimize the sintering treatment time. Trials with glass and paper substrates were performed and proved that IR drying is interesting to optimize sintering. Indeed a similar level of resistance was obtained for conventional heating (200 °C, 5 min) and for IR radiations within a shorter treatment time (3 min). Moreover, the substrate temperature during the IR sintering treatment was controlled. The substrate appears to be a relevant parameter to optimize sintering because its thermal behaviour directly impacts on the treatment duration. And for the first time a sheet resistance of 1.9 Ω sq⁻¹ was obtained on paper substrate after only 2 min of IR treatment without any observation of substrate degradation. The evaluation of an electrical treatment on the sintering of a nanoparticle film was also performed using a corona pre-treatment. This lead appears to be interesting because the study proves that an electrical treatment can initiate the sintering of silver nanoparticles. The current flow generated by the corona electrodes certainly generates a local heating by dissipation of the conductive pattern. Finally, the solutions presented in this article allow reducing the sintering time of silver conductive inkjet inks. However mainly, it proves that using paper as substrate for such inks is now possible.     

Atomized spraying of liquid metal droplets on desired substrate surfaces as a generalized way for ubiquitous printed electronics

A direct electronics printing technique through atomized spraying for patterning room-temperature liquid metal droplets on desired substrate surfaces is proposed and experimentally demonstrated for the first time. This method is highly flexible and capable of fabricating electronic components on various target objects, with either flat or rough surfaces, made of different materials, or having different orientations from 2D to 3D geometrical configurations. With a pre-designed mask, the liquid metal ink can be directly deposited on the substrate to form various specific patterns which lead to the rapid prototyping of electronic devices. Further, extended printing strategies were also suggested to illustrate the adaptability of the method. For example, it can be used for making transparent conductive film with an optical transmittance of 47 % and a sheet resistance of 5.167Ω/□ due to natural porous structure. Different from the former direct writing technology where large surface tension and poor adhesion between the liquid metal and the substrate often impede the flexible printing process, the liquid metal here no longer needs to be pre-oxidized to guarantee its applicability on target substrates. One critical mechanism was that the atomized liquid metal microdroplets can be quickly oxidized in the air due to its large specific surface area, resulting in a significant increase of the adhesion capacity and thus firm deposition of the ink to the substrate. This study paved a generalized way for pervasively and directly printing electronics on various substrates which are expected to be significant in a wide spectrum of electrical engineering areas.     

Surface state control of III–V semiconductors using molecular modification

An attempt to control surface electronics of III–V semiconductor using wet chemical processes has been performed. Here, we report results on the use of self-assembled monolayers (SAMs) of organic molecules on (0 0 1) GaAs surface. Octadecanethiol (ODT) and benzenethiol (BT) have been the choice in the present study.GaAs wafers were modified by thiol molecules on the flat surface after the native oxide layers are removed by chemical etching under optimized conditions. The change in the electronic properties was measured in terms of transport properties via the SAM layer by conductive probe atomic force microscopy. The current–voltage characteristics thus obtained show that ODT functions as a tunnel barrier while BT is conductive due to the presence of π-electrons. As a result, we can control the electronic states of GaAs–molecule interface for realizing novel device structures by the selection of functional molecules.     

Highly Stable Graphene Inks Based on Organic Binary Solvents

Formulating highly stable graphene-based conductive inks with consistency in electrical properties over the storage period has remained a significant challenge in the development of wearable electronics. Two highly stable graphene-based inks (Cyclohexanone:Ethylene glycol (CEG) ink and Cyclohexanone:Terpineol (CT) ink) are prepared by using two different organic binary solvents, for the first time, without using solvent exchange methods. Both the inks display remarkably high stability (stable even after two months) with negligible variability in electrical properties. Here, it is demonstrated how such inks can be utilized to coat flexible substrates to create wearable e-textiles. Both the inks coated e-textiles show significantly low sheet resistance (≈209.1 Ω □⁻¹ for CEG ink and ≈322.4 Ω □⁻¹ CT ink) that show less than a 15% increase in electrical resistance over two months. Therefore, these inks offer high productivity and reproducibility and can be one of the most effective methods for formulating graphene-based inks.     

Synthesis and characterization of copper ink and direct printing of copper patterns by inkjet printing for electronic devices

Among the conventional metallic inks used in the printing process, silver exhibits high conductivity and thermal stability. Nevertheless, due to the high cost of silver, it cannot be extensively used for the fabrication of inks. As a competitive alternative, copper can be considered as a substitute for silver; however, copper ink oxidizes under certain atmospheric conditions. To meet these shortcomings, a cost effective, highly conductive, and oxidation-free copper-based ink has been synthesized in this study, wherein, oxidation of the copper particles in the copper-based ink was prevented by using copper complexes. The copper ink thus fabricated was printed on chemically treated Si/SiO₂ substrates followed by the characterization of the printed copper films. The results of this study confirmed that the synthesized copper ink exhibited properties suitable for its use in the inkjet printing process for fabrication of various electronic devices.     

Percolation of electrical conductivity in solution-cast blends containing polyaniline

The potential offered by intrinsically conductive polymers is limited by their poor mechanical properties. Blending with common thermoplastics can improve processability and mechanical properties and still preserve the electrical conductivity. In such blends, the morphology determines the mechanical and electrical properties. In this research, blends of polyaniline (PANI)-dodecyl benzene sulfonic acid (DBSA) with either polystyrene (PS) in xylene or polyvinylchloride (PVC) in bromobenzene were solution cast. The morphologies of the blends were characterized by optical microscopy (OM), electron microscopy, and small-angle X-ray scattering (SAXS). Electrical conductivity was measured for various compositions. The formation of a continuous network was strongly associated with percolation and conductivity. The morphologies of the two blends are significantly different. This difference arises from the different solvents used and their ability to swell the PAN1 aggregates and to promote their disintegration into small particles. Molecular calculations show that, indeed, bromobenzene, used in the PVC system, is able to penetrate the PANI-DBSA aggregates, while xylene, used in the PS system, cannot. Nevertheless, the small PANI-DBSA particles in the PVC matrix form a conductive network only at a relatively high content, while the coarse aggregates in the PS matrix form conductive paths at a relatively low content. These results are discussed in terms of the formation and stability of the PANI-DBSA dispersion.     

Methods for preparation of transparent conductive diamond-like carbon films and mechanisms of conductivity formation

Technology for obtaining transparent conductive diamond-like carbon films has been developed. Conductivity of the films is ensured by doping with nitrogen during the growth process or by preliminary deposition onto the substrate of a catalyst of nanostructure growth. Optical methods of control of the process which allow varying both the transparency and conductivity of the obtained coatings are described. The mechanisms of formation of conductivity in a dielectric carbon matrix were investigated. It is shown that in the presence of catalysts the conductivity of films can be described using a percolation mechanism.     

Transparent carbon nanotube coatings

Thin networks of carbon nanotubes (CNTs) are sprayed onto glass or plastic substrates in order to obtain conductive transparent coatings. Transparency and conductivity at room temperature of different CNT material are evaluated. CNT coatings maintain their properties under mechanical stress, even after folding the substrate. At a transparency of 90% for visible light we observe a surface resistivity of 1 kΩ/sq which is already a promising value for various applications.     

Study on Surface Oxidative Characterization of LPE HgCdTe Epilayer by X-Ray Photoelectron Spectroscopy

This report presents a surface pre-treatment method of LPE HgCdTe epilayer to reduce and remove the oxides and contaminants. The surface oxidative characterization of LPE HgCdTe epilayer has been studied by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). HgCdTe surface exposed by various processing steps has been measured and analyzed, the results show the native oxide film can be removed by the solution of lactic acid in ethylene glycol after etching by bromine in absolute ethyl alcohol. It indicates that the mainly optical and electrical parameters of LPE HgCdTe epilayer have not been changed. It is evident that the pre-treatment before HgCdTe surface passivation affects the passivant/HgCdTe interface properties.     

First-principles study of the formation and electronic structure of a conductive filament in ZnO-based resistive random access memory

Oxygen vacancy plays a crucial role in resistive switching. To date, a quantitative study about the distribution of the oxygen vacancies and its effect on the resistive switching has not yet been reported. In this study, we report our first-principles calculations in ZnO-based resistive switching memory grown on a Pt substrate. We show that the oxygen vacancies prefer to be located in the ZnO (0001) plane, i.e. in the direction parallel to the film surface in the preparation process. These oxygen vacancies drift easily in the film when a voltage is applied in the SET process and prefer to form a line defect perpendicular to the film surface. An isolated oxygen vacancy makes little contribution to the conductivity of ZnO, whereas the ordering of oxygen vacancies in the direction perpendicular to the film surface leads to a dramatic enhancement of the conductivity and thus forms conductive filaments. The semiconducting characteristics of the conductive filaments are confirmed experimentally.     

Melt-mediated coalescence of solution-deposited ZnO nanoparticles by excimer laser annealing for thin-film transistor fabrication

Nanoparticle solutions are considered promising for realizing low cost printable high performance flexible electronics. In this letter, excimer laser annealing (ELA) was employed to induce melting of solution-deposited ZnO nanoparticles and form electrically conductive porous films. The properties of the films were characterized by scanning electron microscopy, high-resolution transmission electron microscopy, DC conductance, and photoluminescence measurements. Thin-film field-effect transistors have been fabricated by ELA without the use of conventional vacuum or any high temperature thermal annealing processes. The transistors show n-type accumulation mode behavior with mobility greater than 0.1 cm²/V s and current on/off ratios of more than 10⁴. Optimization and control of the laser processing parameters minimized thermal impact on the substrate. This technique can be beneficial in the fabrication of metal oxide based electronics on heat sensitive flexible plastic substrates using low-cost, large-area solution processing combined with direct printing techniques.     

Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries

Li-rich layered oxides (LLOs) have been developed as a high-capacity cathode material for Li-ion batteries, but the structural complexity and unique initial charging behavior lead to several problems including large initial capacity loss, capacity and voltage fading, poor cyclability, and inferior rate capability. Since the surface conditions are critical to electrochemical performance and the drawbacks, nanoscale surface modification for improving LLO’s properties is a general strategy. This review mainly summarizes the surface modification of LLOs and classifies them into three types of surface pre-treatment, surface gradient doping, and surface coating. Surface pre-treatment usually introduces removal of Li₂O for lower irreversible capacity while surface doping is aimed to stabilize the structure during electrochemical cycling. Surface coating layers with different properties, protective layers to suppress the interface side reaction, coating layers related to structural transformation, and electronic/ionic conductive layers for better rate capability, can avoid the shortcomings of LLOs. In addition to surface modification for performance enhancement, other strategies can also be investigated to achieve high-performance LLO-based cathode materials.     

Manufacturing of nanoscale thickness gold lines by laser curing of a discretely deposited nanoparticle suspension

The present work is focused on a novel method for the manufacturing of electric microconductors for semiconductors and other devices. Three different technologies are combined in this technique: controlled (drop on demand) printing, laser curing, and the employment of nanoparticles of matter, possessing markedly different properties (here, melting point) than their bulk counterparts. A modified on demand ink jet process is utilized to print electrically conducting line patterns from a suspension of gold nanoparticles in toluene. Microdroplets of 60–100 μm diameter are generated and deposited on a moving substrate such that the droplets form continuous lines. Focused laser irradiation is utilized in order to evaporate the solvent, melt the metal nanoparticles in the suspension, and sinter the suspended particles to form continuous, electrically conducting gold microlines on a substrate. The ultrafine particles in the suspension have a diameter size range of 2–5 nm. Due to curvature and surface effects of such small particles, the melting point is markedly lower than that of bulk gold (1063 C). Atomic force microscopy and scanning electron microscopy have been employed to investigate the topology of the cured line. In situ visualization of the curing process has been conducted. Results on the effect of the laser irradiation power on the topology and width of the cured line, which is directly related to the electrical conductivity, are reported.     

基片偏压对MCECR溅射硬碳膜特性的影响

采用封闭式电子回旋共振(MCECR)氩等离子体溅射碳靶的方法在硅片上沉积了高质量的硬碳膜, 膜层厚度约40 nm. 使用X射线光电子能谱仪(XPS)和高分辨率透射电子显微镜(HRTEM)分析了碳膜结构,并用POD摩擦磨损仪测试了碳膜的摩擦磨损特性,用纳米压入仪测试了碳膜的纳米硬度.详细研究了基片偏压对碳膜的结构、摩擦磨损特性以及纳米硬度的影响,得到了最佳基片偏压.     

硅基底石墨烯器件的现状及发展趋势

石墨烯是一种由单层碳原子紧密排列而形成的具有蜂窝状结构的二维晶体材料,特殊的结构赋予了其优异的性能,如高载流子迁移率、电导率、热导率、力学强度以及量子反常霍尔效应.由于石墨烯优异的特性,迅速激起了人们对石墨烯研究以及应用的热情.石墨烯沉积或转移到硅片后,其器件构建与集成和传统硅基半导体工艺兼容.基于石墨烯的硅基器件与硅基器件的有机结合,可以大幅度提高半导体器件的综合性能.随着石墨烯制备工艺和转移技术的优化,硅基底石墨烯器件将呈现出潜在的、巨大的实际应用价值.随着器件尺寸的纳米化,器件的发热、能耗等问题成为硅基器件与集成发展面临的瓶颈问题,石墨烯的出现为解决这些问题提供了一种可能的解决方案.本文综述了石墨烯作为场效应晶体管研究的进展,为解决石墨烯带隙为零、影响器件开关比的问题,采用了量子限域法、化学掺杂法、外加电场调节法和引入应力法.在光电器件研究方面,石墨烯可以均匀吸收所有频率的光,其光电性能也受到了广泛的关注,如光电探测器、光电调制器、太阳能电池等.同时,石墨烯作为典型的二维材料,其优越的电学性能以及超高的比表面积,使其作为高灵敏度传感器的研究成为纳米科学研究的前沿和热点领域.     

Plasma-aided hydrogenation and Al-doping: Increasing the conductivity and optical transparency of ZnO transparent conducting oxide

Plasma-assisted magnetron sputtering with varying ambient conditions has been utilised to deposit Al-doped ZnO (AZO) transparent conductive thin films directly onto a glass substrate at a low substrate temperature of 400 °C. The effects of hydrogen addition on electrical, optical and structural properties of the deposited AZO films have been investigated using X-ray diffractometry (XRD), scanning electron microscopy (SEM), Hall effect measurements and UV-vis optical transmission spectroscopy. The results indicate that hydrogen addition has a remarkable effect on the film transparency and conductivity with the greatest effects observed with a hydrogen flux of approximately 3 sccm. It has been demonstrated that the conductivity and the average transmittance in the visible range can increase simultaneously contrary to the effects observed by other authors. In addition, hydrogen incorporation further leads to the absorption edge shifting to a shorter wavelength due to the Burstein-Moss effect. These results are of particular relevance to the development of the next generation of optoelectronic and photovoltaic devices based on highly transparent conducting oxides with controllable electronic and optical properties.